JPH07114178A - Photosensitive lithographic printing plate and plate making method - Google Patents

Abstract

PURPOSE:To obtain a photosensitive lithographic plate without the printing durability being decreased, excellent in sensitivity and developability and capable of erasing the film edge part of an original by providing a positive photosensitive composition layer on a sandblasted and anodically oxidized substrate. CONSTITUTION:A positive photosensitive composition layer contg. an O-quinone diazide compd. alkali-soluble resin and clathrate compd. is provided on a sandblasted and anodically oxidized substrate. The O-quinone diazide compd. is a polycondensed resin having an O-quinone diazide group and >=3000mol.wt., and the clathrate compd. is preferably selected from cyclic D-glucans and cyclophanes. A hydrophilic layer is preferably provided on the substrate which has been sandblasted, anodically oxidized and sealed. This positive photosensitive lithographic printing plate is picture-exposed with a developer contg. alkali metal silicate. As a result, a deposit is not formed in the developer bath.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive-working photosensitive lithographic printing plate and a developing method for the positive-working photosensitive lithographic printing plate.

[0002]

BACKGROUND OF THE INVENTION A photosensitive lithographic printing plate is one in which a photosensitive layer is provided on a hydrophilic support. For example, in a positive type photosensitive lithographic printing plate, an actinic ray such as ultraviolet rays is provided on the hydrophilic support. An ink-receptive photosensitive layer that is solubilized by exposure to is formed.

In such a positive-working photosensitive lithographic printing plate, when the photosensitive layer is imagewise exposed and then developed, the ink-receptive photosensitive layer in the exposed area is removed to expose the surface of the hydrophilic support. On the other hand, the unexposed portion of the photosensitive layer which is ink-receptive remains on the support to form an ink-receptive layer. In lithographic printing, the difference in the property that the exposed portion is hydrophilic and the unexposed portion is lipophilic is used.

Usually, the photosensitive layer of a positive-working photosensitive lithographic printing plate contains a photosensitive composition containing an o-quinonediazide compound as a photosensitive component and an alkali-soluble resin as a component for enhancing film strength and alkali solubility. Things are used.

As the above-mentioned o-quinonediazide compound,
1,2-naphthoquinone-2-diazide-5-sulfonic acid ester compounds and 1,2-naphthoquinone-2-diazide-4-sulfonic acid ester compounds are commonly used as useful compounds, and particularly o-quinonediazide group A polycondensation resin having, for example, an ester compound of a polycondensation resin of pyrogallol and an aldehyde or a ketone is preferably used.

When an ester compound with a polycondensation resin or the like is used as the o-quinonediazide compound, the polycondensation resin usually has a weight molecular weight of 300 in order to improve printing durability.
0 or more resins are used.

Further, a developing method is generally used in which the developing is carried out by replenishing a replenishing developing solution and replenishing the developing solution components consumed by the developing process.

When the positive type photosensitive lithographic printing plate using the o-quinonediazide compound as described above is developed while replenishing the replenishing developer, the replenishing amount of the replenishing developer increases,
When the developing solution becomes tired, when a photosensitive lithographic printing plate is developed using a step tablet for sensitivity measurement (generally, 21 steps of gray scale with a density difference of 0.15 each) as an original The phenomenon occurs that the part corresponding to the halftone part of the step tablet of the planographic printing plate becomes red, and that the part that becomes red cannot be erased with a commonly used erasing liquid (correction liquid). . This phenomenon, in the actual plate making work of the lithographic printing plate, a portion corresponding to the edge portion of the film of the original may remain as an unnecessary image portion on the printing plate,
In that case, the problem arises that the unnecessary image portion cannot be erased. For this reason, the ink is deposited on a portion corresponding to the edge portion of the film that is not properly erased, which causes defective printing, which is a problem.

The occurrence of the above problems is particularly remarkable when a positive photosensitive composition is provided on a support which has been grained and anodized, as in a general photosensitive lithographic printing plate. Further, when an ester compound with a polycondensation resin is used as the o-quinonediazide compound, it is more remarkable.

In order to solve the reddish problem in the halftone part (that is, the problem of erasing failure in the part corresponding to the film edge of the original document), the molecular weight of the polycondensation resin should be lowered, and the organic acid or inorganic acid in the photosensitive layer should be reduced. It is known to add a large amount of acid.

However, the above solution has a problem that the printing durability is lowered, and further improvement has been desired.

Further, as a plate-making method which has good developability even during repeated development processing over a long period of time and does not generate precipitates (sludge) in a developer bath, JP-A-5-22
No. 73, [SiO ₂ ] / [M] is 0.15 to 0.
5 and the SiO ₂ concentration is 1.0 to 3.
Although a method of replenishing with a replenisher composed of an aqueous solution of an alkali metal silicate of 0% by weight for development, JP-A-6-35174 describes a method of providing a back coat layer on the back surface of a grain support. In the case of making a plate by the developing method or the photosensitive lithographic printing plate as described above, the phenomenon that the halftone part of the developed photosensitive lithographic printing plate becomes red occurs and cannot be erased, that is, the film edge part. The problem of erasing failure occurs. The redness of the halftone portion can be reduced by lowering the SiO ₂ concentration of the developer and the development replenisher, but by lowering the SiO ₂ concentration,
This time, there arises a problem that the deposits in the developer bath increase.

Further, by providing a hydrophilic layer on the grain support of the photosensitive lithographic printing plate, the erasing failure at the film edge portion and the generation of deposits in the developing solution bath are somewhat suppressed, The effect was small and insufficient.

[0014]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide good sensitivity without deterioration in printing durability, good developability even in repeated development processing over a long period of time, and to obtain a film edge portion of an original. It is an object of the present invention to provide a positive-working photosensitive lithographic printing plate which can be erased and in which no precipitate is generated in a developer bath, and a development processing method thereof.

[0015]

The above objects of the present invention are as follows: (1) An o-quinonediazide compound, an alkali-soluble resin, a support having been subjected to a graining treatment and an anodic oxidation treatment,
And a positive-type photosensitive composition layer containing an inclusion compound, the photosensitive lithographic printing plate. (2) The photosensitive lithographic printing plate as described in (1) above, wherein the o-quinonediazide compound is a polycondensation resin having an o-quinonediazide group and a molecular weight of 3000 or more. (3) The photosensitive lithographic printing plate as described in (1) or (2) above, wherein the o-quinonediazide compound is a polycondensation resin of an o-quinonediazide group-containing pyrogallol and an aldehyde or a ketone. (4) The photosensitive lithographic printing plate as described in (1) to (3) above, wherein the clathrate compound is at least one selected from cyclic D-glucans and cyclophanes. (5) The photosensitive lithographic printing plate as described in (1) to (4) above, wherein the inclusion compound is at least one selected from cyclodextrin and cyclodextrin derivatives. (6) The photosensitive lithographic printing plate as described in (5) above, wherein the cyclodextrin in the cyclodextrin or cyclodextrin derivative is a β-type cyclodextrin. (7) The photosensitive lithographic printing plate as described in (1) to (6) above, wherein the support is provided with a hydrophilic layer after graining, anodic oxidation and sealing. . (8) A plate-making method characterized by subjecting the positive photosensitive lithographic printing plate described in (1) to (7) above to image exposure and then developing with a developer containing an alkali metal silicate. (9) The development process is [SiO ₂ ] / [M] ([SiO ₂ ]
Indicates the molar concentration of SiO ₂ , and [M] indicates the molar concentration of alkali metal. ) Is 0.15 to 1.0, and SiO
₍₂ ) A method for making a photosensitive lithographic printing plate as described in (8) above, which is carried out using a developer and / or a developer replenisher having a concentration of 0.5 to 5.0% by weight based on the total weight. . Can be achieved by

The present invention will be described in detail below.

First, the orthoquinonediazide compound, the alkali-soluble resin and the clathrate compound used in the positive photosensitive composition layer of the present invention will be described.

The orthoquinonediazide compound used in the positive photosensitive composition layer of the present invention is a compound having an orthoquinonediazide group in its molecule, and the orthoquinonediazide compound usable in the present invention is particularly limited. However, examples thereof include polycondensation resins having an orthoquinonediazide group, such as ester compounds of polycondensation resins of o-naphthoquinonediazide sulfonic acid with phenols and aldehydes or ketones.

Examples of the phenols in the polycondensation resin with the above-mentioned phenols and aldehydes or ketones include phenol, o-cresol, m-cresol,
Examples include monohydric phenols such as p-cresol, 3,5-xylenol, carvacrol, thymol, dihydric phenols such as catechol, resorcin, and hydroquinone, and trihydric phenols such as pyrogallol and phloroglucin. Examples of the aldehyde include formaldehyde,
Examples thereof include benzaldehyde, acetaldehyde, crotonaldehyde, furfural and the like. Of these, preferred are formaldehyde and benzaldehyde. Examples of ketones include acetone and methyl ethyl ketone.

Specific examples of polycondensation resins with phenols and aldehydes or ketones include phenol-formaldehyde resin, m-cresol-formaldehyde resin, m- and p-mixed cresol-formaldehyde resin, resorcin-benzaldehyde resin, Examples include pyrogallol / acetone resin.

In the o-naphthoquinonediazide compound, the condensation rate of o-naphthoquinonediazide sulfonic acid with respect to the OH groups of phenols (reaction rate with respect to one OH group) is preferably 15% to 80%, more preferably 2%.
It is 0% to 45%.

Further, as the orthoquinonediazide compound used in the present invention, the following compounds described in JP-A-58-43451 can also be mentioned. That is, for example, 1,2-benzoquinone diazide sulfonic acid ester, 1,2-naphthoquinone diazide sulfonic acid ester, 1,2-benzoquinone diazide sulfonic acid amide,
Known 1,2-quinonediazide compounds such as 1,2-naphthoquinonediazide sulfonic acid amide, and more specifically, J. Kosar "Light-Sensitive Systems" No. 339. Pp. 352 (1965), John Willie
And Sons (John Willey & Sons) (New York) and W S De Forest (WSDe F)
1,2-benzoquinonediazide-4-sulfonic acid phenyl ester, 1, described in "Photoresist", Vol. 50 (1975), McGraw Hill, Inc. (New York).
2,1 ′, 2′-di- (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-sulfonic acid-4'-hydroxydiphenyl-4 '
-Azo-β-naphthol ester, N, N-di- (1,
2-naphthoquinonediazide-5-sulfonyl) -aniline, 2 '-(1,2-naphthoquinonediazide-5-sulfonyloxy) -1-hydroxy-anthraquinone,
1,2-naphthoquinonediazide-5-sulfonic acid-2,
4-dihydroxybenzophenone ester, 1,2-naphthoquinonediazide-5-sulfonic acid-2,3,4-trihydroxybenzophenone ester, 1,2-naphthoquinonediazide-5-sulfonic acid chloride 2 mol and 4,
Condensate with 1 mol of 4'-diaminobenzophenone, 1,
2-naphthoquinonediazide-5-sulfonic acid chloride 2
, A condensate of 1,4'-dihydroxy-1,1'-diphenylsulfonic acid 1 mol, a condensate of 1,2-naphthoquinonediazide-5-sulfonic acid chloride 1 mol and purpurogallin 1 mol, 1,2 -Naphthoquinone diazide-
A 1,2-quinonediazide compound such as 5- (N-dihydroabietyl) -sulfonamide can be exemplified. In addition, Japanese Examined Patent Publications No. 37-1953 and 37-3627
Nos. 37-13109, 40-26126, 40-3801, 45-5604, 45-27.
No. 345, No. 51-13013, JP-A-48-965.
The 1,2-quinonediazide compounds described in JP-A-75, JP-A-48-63802 and JP-A-48-63803 can also be mentioned.

Of the above orthoquinonediazide compounds,
An o-quinone diazide ester compound obtained by reacting 1,2-benzoquinone diazide sulfonyl chloride or 1,2-naphthoquinone diazide sulfonyl chloride with pyrogallol-acetone condensation resin or 2,3,4-trihydroxybenzophenone is particularly preferable.

In the present invention, as the orthoquinonediazide compound, the above compounds may be used alone or in combination of two or more kinds.

The content of the orthoquinonediazide compound in the photosensitive composition is preferably 5 to 60% by weight, and particularly preferably 10 to 50% by weight.

The alkali-soluble resin that can be used in the present invention is not particularly limited, and examples thereof include novolac resins, vinyl polymers having a phenolic hydroxyl group, and JP-A-55-57841. Examples thereof include condensation resins of polyphenols with aldehydes or ketones.

Examples of the novolac resin that can be used in the present invention include phenol / formaldehyde resin, cresol / formaldehyde resin, JP-A-55.
-57841, a phenol-cresol-formaldehyde copolymer resin, as described in JP-A-55-127553.
Copolymer resins of substituted phenol and phenol or cresol and formaldehyde can be used.

The novolak resin preferably has a number average molecular weight Mn of 3.00 × 10 (polystyrene standard).
^{2 to} 7.50 × 10 ³ , weight average molecular weight Mw of 1.00 ×
10 ^{3 to} 3.00 × 10 ⁴ , more preferably Mn of 5.0
0 × 10 ^{2 to} 4.00 × 10 ³ , Mw of 3.00 × 10 ^3.
˜2.00 × 10 ⁴ .

The above novolak resins may be used alone or in combination of two or more kinds.

The novolac resin is contained in the photosensitive composition in an amount of 5 to 9
It is preferable to contain 5% by weight.

The vinyl polymer having a phenolic hydroxyl group is a polymer having a unit having a phenolic hydroxyl group in its molecular structure, and is represented by the following general formula [I] to
A polymer containing at least one structural unit represented by [V] is preferable.

[0032]

[Chemical 1]

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

The vinyl polymer having a phenolic hydroxyl group used in the present invention preferably has a copolymer type structure having the structural units represented by the general formulas [I] to [V]. As the monomer to be copolymerized,
For example, ethylene, propylene, isobutylene, butadiene, isoprene and other ethylenically unsaturated olefins,
For example, styrenes such as styrene, α-methylstyrene, p-methylstyrene, and p-chlorostyrene, for example,
Acrylic acids such as acrylic acid and methacrylic acid, for example,
Itaconic acid, maleic acid, unsaturated aliphatic dicarboxylic acids such as maleic anhydride, for example, methyl acrylate, ethyl acrylate, acrylate n-butyl, isobutyl acrylate, dodecyl acrylate, 2-chloroethyl acrylate, Phenyl acrylate, α-methyl chloroacrylate, methyl methacrylate, ethyl methacrylate, esters of α-methylene aliphatic monocarboxylic acid such as ethyl ethacrylate, for example, acrylonitrile, nitriles such as methacrylonitrile, for example, acrylamide. Amides such as, for example, acrylanilide, p-chloroacrylanilide, m-nitroacrylanilide, m-
Anilides such as methoxyacrylanilide, for example, vinyl acetate, vinyl propionate, vinyl benzoate, vinyl esters such as vinyl acetate, for example, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, vinyl ethers such as β-chloroethyl vinyl ether, Vinyl chloride, vinylidene chloride, vinylidene cyanide, for example, 1-methyl-1-methoxyethylene, 1,1-dimethoxyethylene, 1,2-dimethoxyethylene, 1,1-dimethoxycarbonylethylene, 1-methyl-1-nitro Ethylene derivatives such as ethylene, for example, N-vinyl-based monomers such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, N-vinylpyrrolidene and N-vinylpyrrolidone. These monomers are present in the polymer compound in a structure in which the unsaturated double bond is cleaved.

Of the above-mentioned monomers, aliphatic monocarboxylic acid esters and nitriles exhibit excellent performance for the purpose of the present invention and are preferred.

These monomers may be bonded to the polymer used in the present invention in either a block or random state.

The vinyl polymer having a phenolic hydroxyl group is preferably contained in the photosensitive composition in an amount of 0.5 to 70% by weight.

As the vinyl polymer having a phenolic hydroxyl group, the above polymers may be used alone or in combination of two or more kinds. It can also be used in combination with other polymer compounds.

The inclusion compound that can be used in the present invention is not particularly limited as long as it is a compound that can incorporate (include) a chemical species, but it is an organic compound soluble in the solvent used for preparing the composition. Is preferred. Examples of such organic compounds include, for example, books such as "Host Guest Chemistry" (written by Michio Hiraoka, Kodansha, 1984, Tokyo) and "Tetrahedron Report" (No. 226 (1)).
987) P5725A. Collet et al.), “Chemical Industry April Issue”
((1991) P278 Shinkai et al.), “Chemical Industry April Issue”
((1991) P288 Hiraoka et al.) And the like.

The inclusion compounds that can be preferably used in the present invention include, for example, cyclic D-glucans, cyclophanes, neutral polyligands, cyclic polyanions, cyclic polycations, cyclic peptides, SPHERANDS, Included are CAVITANDS and their acyclic analogs. Among these, cyclic D-glucans and acyclic analogs thereof, cyclophanes, and neutral polyligands are more preferable.

Examples of the cyclic D-glucans and acyclic analogs thereof include compounds in which α-D-glucopyranose is linked by a glycolide bond.

Examples of the compound include starch, amylose, amylopectin, and other carbohydrates composed of D-glucopyranose groups, α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, and D-glucopyranose polymerization. Cyclodextrins such as cyclodextrin having a degree of 9 or more, and SO ₃ C ₆ H ₄ CH ₂ C ₆ H ₄
SO ₃ group, NHCH ₂ CH ₂ NH group, NHCH ₂ CH ₂ NH
CH ₂ CH ₂ NH group, SC ₆ H ₅ group, N ₃ group, NH ₂ group, NE
t ₂ group, SC (NH ⁺ ₂ ) NH ₂ group, SH group, SCH ₂ CH
_{2 The following} formula in which a substituent such as NH ₂ group, imidazole group, ethylenediamine group is introduced.

[0043]

[Chemical 2] A modified product of D-glucan represented by Further, a cyclodextrin derivative and a branched cyclodextrin represented by the following general formula [VI] and general formula [VII],
Cyclodextrin polymer etc. are also mentioned.

[0044]

[Chemical 3]

In the general formula [VI], R₁~ R₃Is it
They may be the same or different and each is a hydrogen atom or alkyl.
Represents a group or a substituted alkyl group. In particular, R ₁~ R₃Is hydrogen
Atom or hydroxyethyl group, hydroxypropyl
The group is preferably a group of substituted alkyl groups in one molecule.
It is more preferable that the content is 15% to 50%. n
₂Represents a positive integer of 4 to 10.

[0046]

[Chemical 4]

In the general formula [VII], R is hydrogen
Child, -R² -CO₂H, -R² -SO₃H, -R²-NH₂Well
Or -N- (R³)₂(R²Is a straight chain having 1 to 5 carbon atoms or
Represents a branched alkylene group, R³Has 1 to 5 carbon atoms
Represents a linear or branched alkyl group.

The production example of cyclodextrin is "Jo
unal of the American Chemical Society "Vol. 71
P. 354, 1949, "Cheimish Berichte", 9th
Volume 0 Page 2561 1949 Volume 90 25661
Pp. 1957, but is of course not limited to these.

The branched cyclodextrin used in the present invention is a known cyclodextrin in which a water-soluble substance such as glucose, maltose, cellobiose, lactose, sucrose, galactose or glucosamine, or a water-soluble substance such as disaccharide is branched or added. And preferably,
Maltosyl cyclodextrin in which maltose is bound to cyclodextrin (the number of bound molecules in maltose may be 1, 2, 3 or the like) or glucosyl cyclodextrin in which glucose is bound to cyclodextrin (number of bound molecules in glucose Is 1 molecule, 2 molecules,
3 molecules or the like may be used).

Specific synthesis methods of these branched cyclodextrins are described in, for example, Starch Kagaku, Vol. 33, No. 2, 1
Pp. 19-126 (1986), pp. 127-132 (1)
986), Starch Chemistry, Volume 30, No. 2, 231-23.
9 (1983) and the like, and can be synthesized by referring to these known methods. For example, maltosyl cyclodextrin uses cyclodextrin and maltose as raw materials and uses enzymes such as isoamylase and pullulanase. Then, it can be produced by a method of binding maltose to cyclodextrin. Glucosylcyclodextrin can be produced in the same manner.

In the present invention, the branched cyclodextrins preferably used include the following specific exemplified compounds.

[Exemplified Compounds] D-1 α-Cyclodextrin with one molecule of maltose bound D-2 β-Cyclodextrin with one molecule of maltose D-3 γ-Cyclodextrin with one molecule of maltose D-4 malto Α-Cyclodextrin with two molecules of D-sulfate D-5 β-Cyclodextrin with two molecules of maltose D-6 γ-Cyclodextrin with two molecules of maltose D-7 α-Cyclodextrin with three molecules of maltose D-8 β-Cyclodextrin with 3 molecules of maltose D-9 γ-Cyclodextrin with 3 molecules of maltose D-10 α-Cyclodextrin with 1 molecule of glucose D-11 β- with 1 molecule of glucose bonded Cyclodextrin D-12 1 molecule of glucose bound γ-Cyclodextrin D-13 Glucose-bonded 2 molecules α-Cyclodextrin D-14 Glucose-bonded 2 molecules β-Cyclodextrin D-15 Glucose-bonded 2 molecules γ-Cyclodextrin D-16 3 glucose molecules Bound α-cyclodextrin D-17 β-cyclodextrin bound to 3 molecules of glucose D-18 Gamma-cyclodextrin bound to 3 molecules of glucose

Regarding the structures of these branched cyclodextrins, HPLC, NMR, TLC (thin layer chromatography) and INEPT method (Insensitive nuclei enhancer) were used.
Although it has been studied variously by measuring methods such as d by polarization transfer), it has not yet been confirmed even with the current science and technology, and it is in the stage of the estimated structure. However, the fact that each monosaccharide, disaccharide, or the like is bound to cyclodextrin is correct in the above measurement method. Therefore, in the present invention, when the monosaccharide or disaccharide polymolecule is bound to the cyclodextrin, for example, when it is individually bound to each glucose of the cyclodextrin as shown in the following figure, or It includes both those linearly linked to one glucose.

[0054]

[Chemical 5]

In these branched cyclodextrins,
Since the ring structure of existing cyclodextrins is retained as it is, it exhibits the same clathrate action as existing cyclodextrins, and the addition of highly water-soluble maltose or glucose dramatically improves its solubility in water. The feature is that it is improving.

The branched cyclodextrin used in the present invention can be obtained as a commercial product. For example, maltosyl cyclodextrin is commercially available as Isoeryte (registered trademark) manufactured by Shimizu Minato Seito Co., Ltd.

Next, the cyclodextrin polymer used in the present invention will be described.

As the cyclodextrin polymer used in the present invention, those represented by the following general formula [VIII] are preferable.

[0059]

[Chemical 6] The cyclodextrin polymer used in the present invention can be produced by crosslinking cyclodextrin with epichlorohydrin to form a crosslinked polymer.

The cyclodextrin polymer is water-soluble, that is, its solubility in water is 100 ° C. at 25 ° C.
It is preferably 20 g or more per milliliter, and for that purpose, the degree of polymerization n ₂ in the above general formula [VIII] is 3
The cyclodextrin polymer itself has higher water-solubility and the effect of solubilizing the substance as the value becomes smaller.

These cyclodextrin polymers can be synthesized by a general method described in, for example, Japanese Patent Laid-Open No. 61-97025 and German Patent No. 3,544,842.

The cyclodextrin polymer may also be used as an inclusion compound of the cyclodextrin polymer as described above.

Cyclophanes are cyclic compounds having a structure in which aromatic rings are connected by various bonds, and many compounds are known. Examples of cyclophanes include these known compounds. it can.

[0064] As the bond connecting an aromatic ring, for example, a single _{bond, - (CR 1 R 2)} m - _{bond, -O (CR 1 R 2)} m O- _{bond, -NH (CR 1 R 2)} m NH − Bond, − (CR ₁ R ₂ ) _{p
NR 3 (CR 4 R 5)} q - _{bond, - (CR 1 R 2)} p N + R 3 R 4
(CR ₅ R ₆ ) _q -bond,-(CR ₁ R ₂ ) _p S ⁺ R ₃ (CR ₄
R _{5) q} - bond, -CO ₂ - bond, -CONR- bond _{(wherein, R 1, R 2, R} 3, R 4, R 5 and R ₆ may be the same or different, a hydrogen atom Or an alkyl group having 1 to 3 carbon atoms, m, p and q may be the same or different and each represents an integer of 1 to 4) and the like.

Examples of the compound include those represented by the following formulas:

[0066]

[Chemical 7] The following formulas represented by paracyclophanes, tri-o-teimotide and cyclotriveratrylene

[0067]

[Chemical 8] Represented by the following formula represented by orthocyclophanes, metacyclofuphane, calixarene, resorcinol-aldehyde cyclic oligomer, etc.

[0068]

[Chemical 9] Metacyclophanes represented by or the following formula

[0069]

[Chemical 10] The para-substituted phenol acyclic oligomer represented by

Neutral polyligands include crown compounds, cryptands, cyclic polyamines and their acyclic analogs. The compound is known to effectively take in metal ions, but can also effectively take in cationic organic molecules.

Other inclusion compounds include urea, thiourea, deoxycholic acid, dinitrodiphenyl, hydroquinone, o-trithymotide, oxyflavan, dicyanoamminenickel, dioxytriphenylmethane, triphenylmethane, methylnaphthalene, spirochroman, Examples include perhydrotriphenylene, clay minerals, graphite, zeolites (faujasite, chabazite, mordenite, levinite, montmorillonite, halosite, etc.), cellulose, amylose, proteins and the like.

These clathrate compounds may be added as a simple substance, but they improve the solubility of the clathrate compound itself or the clathrate compound incorporating the molecule in a solvent and the compatibility with other additives. For this reason, a polymer in which a substituent having an inclusion ability is suspended as a pendant substituent may be added together with the polymer.

The polymer is, for example, disclosed in JP-A-3-221.
501, JP-A-3-221502, JP-A-3-221503, JP-A-3-221504, and JP-A-3-221505, which can be easily obtained by using the method. You can

Of the above-mentioned clathrate compounds, cyclic and acyclic D-glucans, cyclophanes, and acyclic cyclophane analogs are preferred. More specifically, cyclodextrin, calixarene, resorcinol-aldehyde cyclic oligomer, and para-substituted phenol acyclic oligomer are preferable.

Cyclodextrin and its derivatives are most preferred, and β-cyclodextrin and its derivatives are more preferred.

The proportion of these clathrate compounds in the photosensitive composition is preferably 0.01 to 10% by weight, and 0.1% to
5% by weight is more preferred.

Further, a printout material capable of forming a visible image upon exposure can be added to the positive photosensitive composition layer of the present invention. The printout material is composed of a compound that generates an acid or a free radical upon exposure to light and an organic dye that changes its color tone by interacting with the generated acid or a free radical. Examples of the compound include o-naphthoquinonediazide-4-sulfonic acid halogenide described in JP-A-50-36209 and JP-A-53-36.
No. 223, trihalomethyl-2-pyrone and trihalomethyl-triazine, and o-naphthoquinonediazide-4-sulfonic acid chloride and phenols having an electron-withdrawing substituent described in JP-A-55-6244. Ester compound or amide compound with aniline,
JP-A-55-77742, JP-A-57-1487
Examples of the organic dyes include Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.) and Patent Pure Blue ( Sumitomo Sangoku Chemical Co., Ltd.), Oil Blue # 6
03 (manufactured by Orient Chemical Industry Co., Ltd.), Sudan Blue
II (manufactured by BASF), crystal violet, malachite green, fuchsin, methyl violet, ethyl violet, methyl orange, brilliant green,
Examples thereof include Congo Red, Eosin, Rhodamine 66 and the like.

In addition to the above-mentioned materials, a plasticizer, a surfactant, an organic acid, an acid anhydride and the like can be added to the positive photosensitive composition layer of the present invention, if necessary.

Further, in order to improve the oil sensitivity of the positive photosensitive composition layer of the present invention, for example, p-tert-butylphenolformaldehyde resin, pn-octylphenolformaldehyde resin or It is also possible to add a resin in which these resins are partially esterified with an o-quinonediazide compound.

The positive type photosensitive composition layer of the present invention is formed by applying a coating solution prepared by dissolving or dispersing a photosensitive composition comprising each of these components in a solvent onto a support and drying. You can

Examples of the solvent that can be used to dissolve the photosensitive composition include methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl. Ether, diethylene glycol diethyl ether, diethylene glycol monoisopropyl ether, propylene glycol, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether,
Dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl ethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-1-butanol, ethyl formate, propyl formate, butyl formate, amyl formate, methyl acetate, ethyl acetate, Propyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, methyl lactate, ethyl lactate, dimethylformamide, dimethyl sulfoxide, dioxane,
Acetone, methyl ethyl ketone, cyclohexanone, methyl cyclohexanone, diacetone alcohol, acetylacetone, γ-butyrolactone, diethyl ketone, 4
-Hydroxy-2-butanone and the like can be mentioned. These solvents may be used alone or in admixture of two or more.

The coating method used for coating the surface of the support with the photosensitive composition is a conventionally known method, for example, spin coating, wire bar coating, dip coating, air knife coating, spray coating, air spray coating, Methods such as electrostatic air spray coating, roll coating, blade coating and curtain coating are used. At this time, the coating amount varies depending on the use, but, for example, 0.05 to 5.0 g as solid content.
A coating amount of / m ² is preferred.

Next, the support used for forming the photosensitive lithographic printing plate of the present invention will be described.

The support preferably has flexibility so that it can be set in an ordinary printing machine and can withstand a load applied during printing. For example, a metal plate of aluminum, magnesium, zinc, chromium, iron, copper, nickel or the like, An alloy plate of these metals, or a metal plate coated with chromium, zinc, copper, nickel, aluminum, iron or the like by plating or vapor deposition can be used. Of these, the support is preferably one using aluminum or its alloy.

Various alloys can be used as the aluminum alloy, for example, silicon, copper, manganese, magnesium,
Examples include alloys of metals such as chromium, zinc, lead, bismuth, and nickel with aluminum.

The support made of aluminum or its alloy is usually subjected to a degreasing treatment prior to the graining treatment in order to remove oil and fat components such as rolling oil adhering to the surface of the support. As the degreasing treatment, degreasing treatment using a solvent such as trichlene and thinner, emulsion degreasing treatment using an emulsion of kesilon and triethanol, and the like are used. In addition, an alkaline aqueous solution such as caustic soda can be used for the degreasing treatment. When an alkaline aqueous solution such as caustic soda is used for the degreasing treatment, it is possible to remove stains and oxide films which cannot be removed only by the above degreasing treatment.

The graining treatment of the present invention is a so-called mechanical surface-roughening method of mechanically roughening the surface, a so-called chemical surface-roughening method of chemically selectively dissolving and roughening the surface, and an electrochemical method. The surface can be roughened by a known method such as a so-called electrochemical roughening method.

The mechanical surface roughening method includes, for example, ball polishing, brush polishing, blast polishing, buff polishing, and the like, and the electrochemical surface roughening method includes hydrochloric acid, nitric acid, etc. There is a method of electrolytically treating with an alternating current or a direct current in an electrolytic solution containing the same.

The graining treatment of the present invention can be carried out by any one of these methods or by using two or more methods in combination.

Since smut is formed on the surface of the support obtained by the graining treatment, it is generally preferable to appropriately perform washing with water or alkali etching in order to remove the smut. Examples of such a treatment include the alkali etching method described in Japanese Patent Publication No. 48-28123 and JP-A No. 53-12739.
Examples thereof include a treatment method such as a sulfuric acid desmutting method described in Japanese Patent Publication No. 1994-242242.

The support treated as described above is then anodized. Wear resistance due to anodizing treatment,
The chemical resistance and water retention can be improved. A known method can be used for the anodizing treatment. For example, a method of electrolyzing at a current density of 1 to 10 A / dm ² using an aqueous solution containing sulfuric acid and / or phosphoric acid or the like at a concentration of 10 to 50% is used. Preferably used, but in addition to US Pat.
A method of electrolyzing in sulfuric acid at a high current density, which is described in US Pat. No. 3,511,661.
It is also possible to use the method of electrolyzing with phosphoric acid described in the specification.

The support that has been anodized may be subjected to a pore-sealing treatment, if necessary. These sealing treatments can be carried out by using known methods such as hot water treatment, boiling water treatment, steam treatment, sodium silicate treatment, dichromate aqueous solution treatment, nitrite treatment and ammonium acetate treatment.

The support is preferably provided with a hydrophilic layer. Water-soluble polymers, alkali metal silicates described in U.S. Pat. No. 3,181,461, JP-A-60-149491, and JP-A-63149 are used for forming the hydrophilic layer.
-165183 gazette amino acid and its salt,
Hydroxyl group-containing amines and salts thereof described in JP-A-60-232998, phosphates described in JP-A-62-19494, and monomers having a sulfo group described in JP-A-59-101651. A polymer compound containing a unit can be used, but in the present invention, the following compounds are preferably used. Water-soluble polymer Specific examples thereof include vinyl resins such as PVA (polyvinyl alcohol), modified PVA, PVAP (polyvinylphosphonic acid), polyvinylpyrrolidone, and polyvinylimidazoline and derivatives thereof; polyacrylic acid, polyacrylamide, polyhydroxyethyl acrylate. Acrylic acid-based copolymers such as; polyethyleneimine; maleic acid copolymers; polyethylene glycol polyoxyethylene; polypropylene glycol; polyurethane resin; polyhydroxymethylurea; polyhydroxymethylmelamine resin; soluble starch; CMC (carboxymethylcellulose); Hydroxyethyl cellulose; guar gum; tragacanth gum; xanthan gum; sodium alginate; gelatin and the like. At least one amino group and two or more

[0094]

[Chemical 11] A compound having a group selected from the following or a salt thereof: Examples of the compound having a phosphonic acid group or a salt thereof include 1-aminoethane-1,1-diphosphonic acid and 1-amino-1-phenylmethane-1,1. -Diphosphonic acid, 1-dimethylaminoethane-1,1-diphosphonic acid, 1-dimethylaminobutane-1,1-diphosphonic acid, 1-dimethylaminomethane-1,1-diphosphonic acid, 1-propylaminoethane-1 , 1-diphosphonic acid, 1-butylaminomethane-1,1-diphosphonic acid,
Aminotrimethylenephosphonic acid, ethylenediaminopentamethylenephosphonic acid, ethylenediaminotetramethylenephosphonic acid, diethylenetriaminopentamethylenephosphonic acid, aminotri (2-propylene-2-phosphonic acid) and hydrochlorides, formates, and oxalates of these compounds Examples of the compound having a phosphinic acid group or a salt thereof include a compound in which the phosphonic acid group of the compound having a phosphonic acid group is changed to a phosphinic acid group, or a salt of these compounds, for example, aminotrimethylene. Phosphinic acid and the like, and as the compound having a phosphoric acid group or a salt thereof, a compound in which the phosphonic acid group of the compound having a phosphonic acid group is changed to a phosphoric acid group or a salt of these compounds,
For example, aminotrimethylene phosphoric acid and the like can be mentioned. A compound having at least one amino group and a carboxyl group or a sulfone group or a salt thereof, specific examples thereof include aminoacetic acid, lysine, threonine, serine, aspartic acid, parahydroxyphenylglycine, dihydroxyethylglycine, anthranilic acid, tryptophan, Examples include amino acids such as arginine, aliphatic amino sulfonic acids such as sulfamic acid and cyclohexyl sulfamic acid, and hydrochlorides, formates and oxalates of these compounds. Compounds having at least one amino group and at least one hydroxyl group or salts thereof. Specific examples thereof include monoethanolamine, diethanolamine, trimethanolamine, tripropanolamine, triethanolamine and hydrochlorides and formates of these compounds. , Oxalate and the like. The alkane or its salt alkane having at least two amino groups includes linear, branched and cyclic alkanes.

Particularly preferred is NH ₂ — (CH ₂ ) _n
Is -NH ₂ (n is an integer of 2 to 10).

As a concrete example, ethylenediamine, 1,
3-diaminopropane, 1,4-diaminobutane, 1,
2-diaminopropane, 1,2-diamino-2-methylpropane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,2-diaminocyclohexane, 1,8-diaminooctane , 1,
Examples include 9-diaminononane, 1,10-diaminodecane and their compounds such as hydrochlorides, formates and oxalates.

The positive-working photosensitive lithographic printing plate of the present invention can be prepared by exposing and developing it in a usual manner. For example, a transparent original image having a line image, a halftone dot image, etc. is brought into close contact with the photosensitive surface for exposure, and then the photosensitive layer in the non-image area is removed using an appropriate developing solution to obtain a relief image. .

Light sources suitable for exposure include mercury lamps, metal halide lamps, xenon lamps, chemical lamps,
Examples include carbon arc lamps. Further, as the developing solution and the developing replenishing solution used for the development, an alkaline aqueous solution is preferable, and examples thereof include alkali metal silicates such as sodium silicate and potassium silicate, sodium hydroxide, potassium hydroxide, trisodium phosphate, An alkaline aqueous solution such as an aqueous solution of sodium diphosphate, sodium carbonate, potassium carbonate or the like can be used.

In the present invention, both the developing solution and the developing replenishing solution used for developing the photosensitive lithographic printing plate contain an alkali metal silicate. The alkali metal of the alkali metal silicate includes lithium, sodium and potassium, and potassium is the most preferable.

At the time of development, it is preferred that the development replenisher is appropriately replenished in accordance with the development processing amount of the photosensitive lithographic printing plate.

Preferred developing solutions and developing replenishers are [SiO 2
₂ ] / [M] (wherein [SiO ₂ ] indicates the molar concentration of SiO ₂ and [M] indicates the molar concentration of alkali metal) is 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. Further, it is particularly preferable that the developing solution [SiO
₂ ] / [M] is 0.25 to 0.75, the SiO ₂ concentration is 1.0 to 4.0% by weight, and the development replenisher [SiO ₂ ] /
[M] is 0.15 to 0.5, and the SiO ₂ concentration is 1.
It is 0 to 3.0% by weight.

The pH of the developing solution and the developing replenishing solution is preferably 12 to 13.8.

The above-mentioned developers and development replenishers may contain water-soluble or alkali-soluble organic and inorganic reducing agents.

Examples of organic reducing agents include phenol compounds such as hydroquinone, metol and methoxyquinone, amine compounds such as phenylenediamine and phenylhydrazine, and examples of inorganic reducing agents include:
For example, sodium sulfite, potassium sulfite, ammonium sulfite, sodium hydrogen sulfite, sulfite salts such as potassium hydrogen sulfite, sodium phosphite, potassium phosphite, sodium hydrogen phosphite, potassium hydrogen phosphite,
Examples thereof include phosphites such as sodium dihydrogen phosphite and dipotassium hydrogen phosphite, hydrazine, sodium thiosulfate, and sodium dithionite.

The water-soluble or alkali-soluble reducing agent can be contained in the developing solution and the developing replenishing solution in an amount of 0.05 to 10% by weight.

Further, the developer and the development replenisher may contain an organic acid carboxylic acid.

These organic acid carboxylic acids include aliphatic carboxylic acids having 6 to 20 carbon atoms, and aromatic carboxylic acids having a benzene ring or naphthalene ring substituted with a carboxyl group.

The fat-proof carboxylic acid has 6 to 2 carbon atoms.
Alkanoic acid of 0 is preferable, and specific examples thereof include caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, mistyric acid, palmitic acid,
Examples thereof include stearic acid and the like, and particularly preferable are alkanoic acids having 6 to 12 carbon atoms. The fat-proof carboxylic acid may be a fatty acid having a double bond in the 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 the aromatic carboxylic acid 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 can be mentioned.

The above aromatic carboxylic acid may be used as a sodium or potassium salt or an ammonium salt.

The content of the aliphatic carboxylic acid and the aromatic carboxylic acid may be at least 0.1 to 30% by weight.

The developer and development replenisher may contain the following anionic, nonionic and cationic surfactants and organic solvents.

As the anionic surfactant, higher alcohol (C ₆ -C ₂₂ ) sulfate ester salts [eg, sodium salt of lauryl alcohol sulfate, sodium salt of octyl alcohol sulfate, ammonium salt of lauryl alcohol sulfate, “Τeepol”]
-81 "(trade name, manufactured by Shell Chemical Co., Ltd., secondary sodium alkylsulfate, etc.), aliphatic alcohol phosphate ester salts (for example, sodium salt of cetyl alcohol phosphate ester), alkylaryl sulfonates ( For example, dodecylbenzene sulfonic acid sodium salt, isopropyl naphthalene sulfonic acid sodium salt, dinaphthalene disulfonic acid sodium salt, metanitrobenzene sulfonic acid sodium salt, etc., alkyl amide sulfonates (eg, C ₁₇ H ₃₃ CON
(CH ₃ ) CH ₂ SO ₃ Na and the like, sulfonates of dibasic fatty acid ester (for example, dioctyl sodium sulfosuccinate, dihexyl sodium sulfosuccinate, etc.). Among these, sulfonates are particularly preferably used.

As the nonionic surfactant, both polyethylene glycol type and polyhydric alcohol type can be used.

Examples of nonionic surfactants include:
Examples thereof include compounds represented by the following general formulas [1] to [8].

[0116]

[Chemical 12] In the general formulas [1] to [8], R is a hydrogen atom or 1
Represents a valent organic group, and a, b, c, m, n, x and y each represent an integer of 1 to 40.

Examples of the organic group represented by R include a linear or branched alkyl group having 1 to 30 carbon atoms, an alkyl group having a substituent [for example, an aryl group (phenyl etc.)], and an alkyl moiety. Straight or branched carbon number 1-3
Examples thereof include an alkylcarbonyl group which is an alkyl group of 0, a phenyl group which may have a substituent (for example, a hydroxyl group, the above-mentioned alkyl group and the like) and the like.

Specific examples of the nonionic surfactant are shown below.

Polyethylene glycol, polyoxyethylene lauryl ether, polyoxyethylene nonyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene behenyl ether,
Polyoxyethylene polyoxypropylene cetyl ether, polyoxyethylene polyoxypropylene behenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene stearyl amine, polyoxyethylene oleyl amine, polyoxyethylene stearic acid amide, Polyoxyethylene oleic acid amide, polyoxyethylene castor oil, polyoxyethylene abiethyl ether, polyoxyethylene lanolin ether, polyoxyethylene monolaurate, polyoxyethylene monostearate, polyoxyethylene glyceryl monooleate, polyoxyethylene Glyceryl monostearate, polyoxyethylene propylene glycol monostearate, oxyethyl Oxypropylene block polymer, distyrenated phenol polyethylene oxide adduct, tribenzylphenol polyethylene oxide adduct, octylphenol polyoxyethylene polyoxypropylene adduct, glycerol monostearate, sorbitan monolaurate, polyoxyethylene sorbitan monolaurate, etc. .

The weight average molecular weight of the nonionic surfactant is preferably in the range of 300 to 10,000. The concentration of the nonionic surfactant in the developer is at least 0.001-10.
It can be wt%.

Cationic surfactants are roughly classified into amine type and quaternary ammonium salt type, and any of these can be used.

Examples of the amine type include polyoxyethylene alkylamine, N-alkyl propylene amine, N
-Alkyl polyethylene polyamine, N-alkyl polyethylene polyamine dimethyl sulfate, alkyl biguanide, long-chain amine oxide, alkyl imidazoline, 1-
Hydroxyethyl-2-alkylimidazoline, 1-acetylaminoethyl-2-alkylimidazoline, 2-
Alkyl-4-methyl-4-hydroxymethyloxazoline and the like can be mentioned.

Examples of the quaternary ammonium salt type are long-chain primary amine salt, alkyltrimethylammonium salt, dialkyldimethylethylammonium salt, alkyldimethylammonium salt, alkyldimethylbenzylammonium salt, alkylpyridinium salt, and alkylquinone. Norinium salt, alkylisoquinolinium salt, alkylpyridinium sulfate, stearamidomethylpyridinium salt, acylaminoethyldiethylamine salt, acylaminoethylmethyldiethylammonium salt, alkylamidopropyldimethylbenzylammonium salt, fatty acid polyethylene polyamide, acylamino Ethylpyridinium salt, Acylcholaminoformylmethylpyridinium salt, Stearooxymethylpyridinium salt, Fatty acid triethanolamine, Fat Acid triethanolamine formate, trioxyethylene fatty acid triethanolamine,
Examples thereof include fatty acid dibutylaminoethanol, cetyloxymethylpyridinium salt, and p-isooctylphenoxyethoxyethyldimethylbenzil ammonium salt. ("Alkyl" in the examples of the above compounds has 6 carbon atoms.
~ 20 straight chain or partially substituted alkyl,
Specifically, straight chain alkyl such as hexyl, octyl, cetyl, stearyl is preferably used. ) Further, a cationic surfactant of a polymer having a cation component as a partitioning unit, for example, a polymer containing a quaternary ammonium salt obtained by copolymerization with a lipophilic monomer can be contained.

The amount of the cationic surfactant added to the developer may be at least 0.001 to 10% by weight.

The weight average molecular weight is at least 300-
Those in the range of 50,000 can be used.

As the surfactant, it is preferable to use a fluorinated surfactant containing a perfluoroalkyl group in the molecule. As such a fluorine-based surfactant,
Perfluoroalkyl carboxylate, perfluoroalkyl sulfonate, anion type such as perfluoroalkyl phosphate, amphoteric type such as perfluoroalkyl betaine, cation type such as perfluoroalkyltrimethylammonium salt and perfluoroalkylamine oxide, Perfluoroalkyl ethylene oxide adduct, oligomer containing perfluoroalkyl group and hydrophilic group, oligomer containing perfluoroalkyl group and lipophilic group, oligomer containing perfluoroalkyl group, hydrophilic group and lipophilic group, perfluoroalkyl group and parent A nonionic type such as an oily group-containing urethane may be mentioned.

The above surfactants can be used alone or in combination of two or more kinds.

As the organic solvent, those having a solubility in water at 20 ° C. of not more than 10% by weight are preferable, and examples thereof include ethyl acetate, propyl acetate, butyl acetate, benzyl acetate, ethylene glycol monobutyl acetoate, butyl lactate, and levulinic acid. Carboxylic acid esters such as butyl;
Ketones such as ethyl butyl ketone, methyl isobutyl ketone, cyclohexanone; such as ethylene glycol monobutyl ether, ethylene glycol benzyl ether, ethylene glycol monophenyl ether, benzyl alcohol, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol Alcohols; alkyl-substituted aromatic hydrocarbons such as xylene; halogenated hydrocarbons such as methylene dichloride, ethylene dichloride and monochlorobenzene.

These organic solvents may be used alone or in combination of two or more.

Further, the following additives can be added to the developer and the development replenisher in order to enhance the developing performance. Examples of these additives include, for example, JP-A-58-7.
Neutral salts such as NaCl, KCl and KBr described in JP-A-5152, EDT described in JP-A-59-190952
Chelating agents such as A and NTA, JP-A-59-121336
[Co (NH ₃ )] ₆ , Cl _{3 and} other complexes described in JP-A-56-142528, amphoteric polymer electrolytes such as copolymers of vinylbenzyltrimethylammonium chloride and sodium acrylate described in JP-A-56-142528, and Kaisho 58-59
Inorganic lithium compounds such as lithium chloride described in Japanese Patent Publication No. 444,444, Organic lithium compounds such as lithium benzoate described in Japanese Patent Publication No. 50-34442, JP-A-59-75255
Organometallic surfactants containing Si, Ti, etc.,
The organic boron compounds described in JP-A-59-84241 are mentioned.

Further, known additives can be added to the developer and the development replenisher.

[0132]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Example 1 [Preparation of support 1] An aluminum plate having a thickness of 0.3 mm (material: 1050, temper H16) was subjected to a degreasing treatment for 1 minute in a 5% sodium hydroxide aqueous solution kept at 65 ° C. ,
It was washed with water, immersed in a 10% sulfuric acid aqueous solution kept at 25 ° C. for 1 minute for neutralization, and further washed with water. The aluminum plate was electrolytically surface-roughened with an alternating current in a 1.0 wt% hydrochloric acid aqueous solution under the conditions of a temperature of 25 ° C., a current density of 100 A / dm ² , and a treatment time of 60 seconds. Then, desmutting treatment is performed in a 5% aqueous sodium hydroxide solution at 60 ° C. for 10 seconds, and then anodization is performed in a 20% sulfuric acid solution at a temperature of 20 ° C., a current density of 3 A / dm ² , and a treatment time of 1 minute. Processed. Then, it was immersed in a 1% sodium nitrite aqueous solution kept at 80 ° C. for 30 seconds, washed with water, and dried at 80 ° C. for 3 minutes. Further, after immersing in an aqueous solution of carboxymethylcellulose (concentration: 0.1% by weight) kept at 85 ° C. for 30 seconds, it was dried at 80 ° C. for 5 minutes to prepare a support 1. [Preparation of support 2] An aluminum plate (material 1050, temper H16) having a thickness of 0.3 mm was degreased for 1 minute in a 5% aqueous sodium hydroxide solution kept at 65 ° C.
It was washed with water, immersed in a 10% sulfuric acid aqueous solution kept at 25 ° C. for 1 minute for neutralization, and further washed with water. The aluminum plate was electrolytically surface-roughened with an alternating current in a 1.0 wt% hydrochloric acid aqueous solution under the conditions of a temperature of 25 ° C., a current density of 100 A / dm ² , and a treatment time of 60 seconds. Then, desmutting treatment is performed in a 5% aqueous sodium hydroxide solution at 60 ° C. for 10 seconds, and then anodization is performed in a 20% sulfuric acid solution at a temperature of 20 ° C., a current density of 3 A / dm ² , and a treatment time of 1 minute. Processed. Then, it was immersed in a 1% sodium nitrite aqueous solution kept at 80 ° C. for 30 seconds, washed with water, and then dried at 80 ° C. for 3 minutes to prepare a support 2.

[Preparation of photosensitive lithographic printing plate sample] Support 1
The following coating solutions described in Table 1 were applied using a wire bar and dried at 80 ° C. for 2 minutes to obtain photosensitive lithographic printing plate samples to and photosensitive lithographic printing plate comparative samples. (Coating liquid 1) Novolac resin (phenol / m-cresol / p-cresol molar ratio 10/54/36, weight average molecular weight 4000) 6.7 g Pyrogallol acetone resin (weight average molecular weight shown in Table 1) and o-naphthoquinone Condensate of diazide-5-sulfonyl chloride (esterification rate 30%) 1.5 g Polyethylene glycol # 2000 0.2 g Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) 0.08 g 2,4-bis (trichloromethyl) -6- (P-Methoxystyryl) -s-triazine 0.15 g FC-430 (Sumitomo 3M Co., Ltd.) 0.03 g cis-1,2-cyclohexanedicarboxylic acid 0.2 g Inclusion compound shown in Table 1 0.2 g Methyl cellosolve 100 ml

(Coating liquid 2) Novolak resin (phenol / m-cresol / p-cresol molar ratio 10/54/36, weight average molecular weight 4000) 6.7 g m-cresol formaldehyde resin (weight average molecular weight 3000) and o -Condensation product of naphthoquinone diazide-5-sulfonyl chloride (esterification rate 30%) 1.5 g Polyethylene glycol # 2000 0.2 g Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) 0.08 g 2,4-bis (trichloromethyl)- 6- (p-methoxystyryl) -s-triazine 0.15 g FC-430 (Sumitomo 3M Ltd.) 0.03 g cis-1,2-cyclohexanedicarboxylic acid 0.2 g Inclusion compound shown in Table 1 0.2 g Methylcellosolve 100 ml

[0135]

[Table 1]

[0136]

[Chemical 13]

With respect to the above samples to and comparative samples, the sensitivity, the erasability of the film edge portion, and the printing durability were evaluated by the following evaluation methods. [Evaluation Method] <Evaluation of sensitivity> A step tablet for sensitivity measurement (Eastman Kodak No. 2, 21-step gray scale with a concentration difference of 0.15 each) was attached to the sample, and a 4 kW metal halide lamp (Dainippon Vio Qui made by Sleeen Co., Ltd.
ck) was used as a light source and exposed from a distance of 90 cm. Next, this sample was developed with the following developing solution A at 30 ° C. for 12 seconds.

The sensitivity was defined as the exposure time at which 3.0 steps of the step tablet was completely cleared.

<Evaluation of erasability of film edge portion> A step plate (No. 2 manufactured by Eastman Kodak Co., Ltd., a density difference of 0.15 for each step) was added to a photosensitive lithographic printing plate.
It was exposed from a distance of 90 cm using a 4 kW metal halide lamp (Vio Quick manufactured by Dainippon Screen Co., Ltd.) as a light source while closely adhering to a one-stage gray scale. Next, this sample was developed with the following developing solution B at a developing temperature of 30 ° C. for a developing time of 12 seconds and washed with water. Further, the step portion was erased with an erasing liquid (SIR-16, manufactured by Konica Corporation). The resulting printing plate is coated with developing ink (SPO-1, made by Konica),
The erasability was evaluated according to the following evaluation criteria.

Evaluation Criteria ○: No ink is attached ×: Ink is attached

<Evaluation of printing durability> A step tablet for sensitivity measurement (No. 2, Eastman Kodak Company, 21-step gray scale with a density difference of 0.15) was attached to the sample, and a 4 kW metal halide lamp (large) was attached. Exposure was carried out from a distance of 90 cm using Vio Quick manufactured by Japan Slene Co., Ltd. as a light source. Next, this sample was treated with the following developer A at 30 ° C. for 12 hours.
Developed for seconds.

The obtained lithographic printing plate was 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 Co., Ltd.) were used. 2.5%) was used for printing, and printing was continued until defective solidification of the image area of the printed matter or ink was applied to the non-image area, and the number of printed sheets at that time was counted.

[Developer formulation] <Formulation of developer A> A potassium silicate aqueous solution (manufactured by Nippon Kagaku Kogyo Co., Ltd.) 75 g potassium hydroxide aqueous solution (50%) 55 g pure water 850 g [SiO ₂ ] / [K] ( Molar ratio) 0.55 SiO ₂ (wt%) 2.0 pH = 12.8 <Developer B formulation> A potassium silicate aqueous solution (Nippon Kagaku Kogyo Co., Ltd.) 110 g potassium hydroxide aqueous solution (50%) 90 g pure water 800 g [SiO ₂ ] / [K] (molar ratio) 0.50 SiO ₂ (wt%) 3.0 pH = 13.0 The evaluation results are shown in Table 2.

[0144]

[Table 2]

Example 2 [Preparation of photosensitive lithographic printing plate sample] Coating liquid 3 or coating liquid 4 described below was applied to support 1 or 2 described in Example 1, and a wire bar was used as shown in Table 3. To obtain a photosensitive lithographic printing plate sample and a comparative sample. (Coating liquid 3) Novolac resin (phenol / m-cresol / p-cresol molar ratio 10/54/36, weight average molecular weight 4000) 6.7 g Pyrogallol acetone resin (weight average molecular weight 3000) and o-naphthoquinone diazide-5 -Sulfonyl chloride condensate (esterification rate 30%) 1.5 g Polyethylene glycol # 2000 0.2 g Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) 0.08 g 2,4-bis (trichloromethyl) -6- (p- Methoxystyryl) -s-triazine 0.15 g FC-430 (Sumitomo 3M Ltd.) 0.03 g cis-1,2-cyclohexanedicarboxylic acid 0.2 g Hydroxypropyl-β-cyclodextrin 0.2 g Methylcellosolve 100 ml (Coating liquid 4 ) Novolac resin (molar ratio of phenol / m-cresol / p-cresol 10/54/36 with a weight average molecular weight of 4000) 6.7 g Pyrogallol acetone resin (weight average molecular weight of 3000) and o-naphthoquinone diazide-5-sulfonyl chloride condensate (esterification rate 30%) 1.5 g Polyethylene glycol # 2000 0.2 g Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.) 0.08 g 2,4-bis (trichloromethyl) -6- (p-methoxystyryl) -s-triazine 0.15 g FC-430 (Sumitomo 3M (stock) )) 0.03 g cis-1,2-cyclohexanedicarboxylic acid 0.2 g methyl cellosolve 100 ml

[0146]

[Table 3] An original film containing a step tablet for sensitivity measurement was brought into close contact with the obtained sample and exposed for 25 seconds from a distance of 90 cm using a 4 kW metal halide lamp (Vio Quick manufactured by Dainippon Screen Co., Ltd.) as a light source. This sample was run up to 100 m ² / liter using the following developing solutions A, C, D and E. At that time, the following developing replenishers A, C,
D and E were supplemented.

[Developer Solution Formulation] <Developer Solution A Formulation> Formulation of Developer Solution A in Example 1 <Developer Solution C Formulation> A Potassium Silicate Aqueous Solution (Nippon Kagaku Kogyo Co., Ltd.) 180 g Potassium Hydroxide Solution (50%) 40 g Pure water 750 g [SiO ₂ ] / [K] (molar ratio) 0.9 SiO ₂ (wt%) 5.0 pH = 12.5

<Formulation of Developer D> A potassium silicate aqueous solution (manufactured by Nippon Kagaku Kogyo Co., Ltd.) 30 g potassium hydroxide aqueous solution (50%) 28 g propylene glycol 20 g p-tert-butylbenzoic acid 5 g triethanolamine 10 g potassium sulfite Aqueous solution (50%) 30 g Perex NBL 5 g EDTA 0.5 g Gluconic acid aqueous solution (50%) 10 g Emulgen 147 (manufactured by Kao Corporation) 2 g Pure water 800 g [SiO ₂ ] / [K] (molar ratio) 0.4 SiO ₂ (weight) %) 0.8 pH = 12.9

<Formulation of Developer E> A potassium silicate aqueous solution (manufactured by Nippon Kagaku Kogyo Co., Ltd.) 240 g potassium hydroxide aqueous solution (50%) 100 g pure water 660 g [SiO ₂ ] / [K] (molar ratio) 0.85 SiO ₂ (wt%) 6.5 pH = 12.8

[Development Replenisher Solution Formulation] <Development Replenisher Solution A Formulation> A Potassium silicate aqueous solution (manufactured by Nippon Kagaku Kogyo Co., Ltd.) 40 g Potassium hydroxide aqueous solution (50%) 90 g Activator 1 [SiO ₂ ] / [K ] (Molar ratio) 0.2 SiO ₂ (wt%) 1.0 pH = 13.3

<Formulation of Development Replenisher C> A Potassium silicate aqueous solution (manufactured by Nippon Kagaku Kogyo Co., Ltd.) 170 g Potassium hydroxide aqueous solution (50%) 140 g Pure water 700 g [SiO ₂ ] / [K] (molar ratio) 0.4 SiO ₂ (wt%) 4.5 pH = 13.8

<Formulation of Development Replenisher D> A potassium silicate aqueous solution (manufactured by Nippon Kagaku Kogyo KK) 30 g Potassium hydroxide aqueous solution (50%) 56 g Propylene glycol 19 g p-tert-butylbenzoic acid 10 g Triethanolamine 15 g Sulfurous acid Aqueous potassium solution (50%) 65 g Perex NBL 5 g EDTA 0.5 g Gluconic acid aqueous solution (50%) 9 g Emulgen 147 (manufactured by Kao Corporation) 2 g Pure water 700 g [SiO ₂ ] / [K] (molar ratio) 0.25 SiO ₂ ( Wt%) 0.9 pH = 13.4

<Formulation of Development Replenisher E> A Potassium silicate aqueous solution (manufactured by Nippon Kagaku Kogyo Co., Ltd.) 225 g Potassium hydroxide aqueous solution (50%) 190 g Pure water 580 g [SiO ₂ ] / [K] (molar ratio) 0.5 SiO ₂ (wt%) 6.0 pH = 13.3 For each sample, PS plate automatic development processor PSZ-91
0 (manufactured by Konica Corp.) was treated with 100 m ² / liter while maintaining the sensitivity constant with the developing solution and the developing replenisher shown in Table 4. After 100 m ² / liter treatment, each sample was evaluated for erasability at the film edge portion in the same manner as in Example 1, and the weight of the precipitate was measured by the following evaluation method to evaluate the occurrence of the precipitate. .

The results obtained are shown in Table 4. [Evaluation Method] <Measurement of Weight of Precipitate> Especially 100 ml of the treatment fatigue liquid at the time of treatment of 10 m ² / liter of each sample was left for 2 weeks and then filtered by suction filtration to sufficiently remove the precipitate remaining on the filter paper. After washing, it was dried and weighed.

<Evaluation of Precipitate Generation Condition> After processing 100 m ² / l, the condition of precipitate generation in the tank and the easiness of flushing were visually evaluated when the automatic processor was washed. Evaluation criteria ○: Almost no precipitates were found in the tank, and easily washed off with water. △: Precipitates were found in the tank, but washed off with water ×: Precipitates were formed in the tank. Are found in large quantities and are difficult to remove with water

[0156]

[Table 4]

[0157]

EFFECT OF THE INVENTION The photosensitive lithographic printing plate of the present invention has no deterioration in printing durability, has good sensitivity, has good developability even after repeated development for a long time, and has a film edge of an original. The part can be erased and no precipitate is generated in the developer bath.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shinichi Matsubara 1 Sakura-cho, Hino-shi, Tokyo Konica Co., Ltd. (72) Inventor Mitsuru Sasaki 1000 Kamoshida-cho, Midori-ku, Yokohama-shi, Kanagawa Sanryo Kasei Co., Ltd. In-house (72) Inventor Katsuko Ota 1000 Kamoshida-cho, Midori-ku, Yokohama, Kanagawa Sanryo Kasei Co., Ltd. In the laboratory

Claims (9)

[Claims] 1. A positive type photosensitive composition layer containing an o-quinonediazide compound, an alkali-soluble resin, and an inclusion compound is provided on a support which has been subjected to graining treatment and anodic oxidation treatment. Photosensitive lithographic printing plate. 2. The photosensitive lithographic printing plate according to claim 1, wherein the o-quinonediazide compound is a polycondensation resin having an o-quinonediazide group and having a molecular weight of 3000 or more. 3. The photosensitive lithographic printing plate according to claim 1, wherein the o-quinonediazide compound is a polycondensation resin of pyrogallol having an o-quinonediazide group and an aldehyde or a ketone. 4. The photosensitive lithographic printing plate as claimed in claim 1, wherein the clathrate compound is at least one selected from cyclic D-glucans and cyclophanes. 5. The photosensitive lithographic printing plate according to claim 1, wherein the clathrate compound is at least one selected from cyclodextrin and cyclodextrin derivatives. 6. The photosensitive lithographic printing plate according to claim 5, wherein the cyclodextrin in the cyclodextrin or the cyclodextrin derivative is β-type cyclodextrin. 7. The photosensitive lithographic printing plate according to claim 1, wherein the support is provided with a hydrophilic layer after graining, anodizing, and sealing. 8. A plate-making method, which comprises exposing the positive-working photosensitive lithographic printing plate according to any one of claims 1 to 7 to an image and then developing it with a developer containing an alkali metal silicate. 9. The development treatment is [SiO ₂ ] / [M]
([SiO ₂ ] indicates the molar concentration of SiO ₂ , and [M] indicates the molar concentration of alkali metal) is 0.15 to 1.0, and the SiO ₂ concentration is 0.5 based on the total weight. 9. The plate-making method for a photosensitive lithographic printing plate according to claim 8, which is carried out using a developing solution and / or a developing replenishing solution in an amount of ˜5.0 wt%.