JPH0968810A - Developing method of photosensitive planographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a planographic printing plate having enough image strength by using a developer of high safeness by developing the plate with an alkali soln. of specified pH and containing a compd. selected from silicic acid, phosphoric acid, carbonic acid, boric acid and sugars. SOLUTION: A printing plate is developed with an alkali soln. containing a compd. selected from silicic acid, phosphoric acid, carbonic acid, boric acid, phenols, sugars, oxims and fluorinated alcohols and having pH12.0 to 13.0. As for a weak acid material such as phenols, sugars, oxims and fluorinated alcohols, a compd. having 10.0-13.2 dissociation const. (pKa) is preferable. As for sugars, a non-reducing sugar which is stable in an alkali is preferable. The proportion of these acid compds. in the developer is preferably about 0.1-30wt.%, and more preferably 1-20wt.%. The combination of the acid compd. and a base may be added in a form of a salt preliminarily prepared, for example, such as potassium silicate.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for treating a photosensitive lithographic printing plate.

[0002]

2. Description of the Related Art Conventionally widely used positive-working photosensitive lithographic printing plates are provided on an aluminum plate as a support.
-A photosensitive layer made of a quinonediazide compound is provided. It is known that an o-quinonediazide compound is converted into a carboxylic acid upon exposure to ultraviolet light. Therefore, when the o-quinonediazide compound is developed with an aqueous alkali solution, only the exposed portion of the photosensitive layer is removed and the surface of the support is exposed. Since the surface of the aluminum support is hydrophilic, a portion (non-image portion) where the surface of the support is exposed by development retains water and repels oil-based ink. On the other hand, the area (image area) where the photosensitive layer has not been removed by the development is lipophilic and thus repels water and receives ink. In the photosensitive layer of these positive type photosensitive lithographic printing plates, a cresol novolac resin has been usually used as a binder (hereinafter referred to as a binder) of the above-mentioned o-quinonediazide compound. Therefore, it has been common to use a strong alkaline silicate having a pH of 13 or more, which can dissolve the cresol novolac resin, as the developer.

Various alkaline aqueous solutions are known to be used as developers for such positive-working photosensitive lithographic printing plates, but most commonly used are silicic acids such as sodium silicate and potassium silicate. It is an aqueous salt solution. The reason is that the ratio of silicon oxide SiO ₂ which is a component of silicate and alkali metal oxide M ₂ O (generally [SiO ₂ ] / [M ₂ O]
This is because the developability can be adjusted to some extent depending on the concentration and the concentration. In addition, almost all positive-working photosensitive lithographic printing plates require a strong alkali having a pH of 13 or more for development, and the silicate exhibits a good buffering action in the pH range, and stable development can be performed. These silicates are not limited to the positive-working photosensitive lithographic printing plates described above, but also a reversal type negative-working photosensitive lithographic printing plate using an o-quinonediazide photosensitive layer described in JP-B-56-14970 and an alkali-soluble diazonium salt. As a developer for a negative photosensitive lithographic printing plate using as a photosensitive layer, and also as a developer for a negative photosensitive lithographic printing plate using a photosensitive layer having a photocrosslinking agent containing a dimethylmaleimide group as a side chain. Used, especially negative type
It has also been used as a common processing developer for positive-working photosensitive lithographic printing plates.

However, such a high pH developer has strong irritation when it adheres to the skin or mucous membranes, and thus requires careful handling. In order to solve this problem, various studies have been made to lower the pH of the developer for a positive photosensitive lithographic printing plate. For example, it has been attempted to use a resin having a high acid value and soluble even at a low pH, as a binder of a photosensitive layer of a positive photosensitive lithographic printing plate, instead of a cresol novolac resin. However, the unexposed area (image area) of the photosensitive layer made of a resin having a high acid value is physically fragile and wears quickly during printing, and sufficient printing durability cannot be obtained. Also, the image area is chemically weak, and the image of the area wiped with an ink cleaning solvent or plate cleaner is damaged during printing, resulting in sufficient printing durability (hereinafter referred to as chemical resistance). Has not been obtained. Furthermore, when an alkali metal silicate is used as the main component of the developer, the pH is 12.
When it is 0 or less, silica gel is likely to be generated, and there is a problem that silica dust is generated in the automatic processor.

[0005]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a developing solution having relatively low irritation to skin and mucous membranes and improved safety. Further, the object of the present invention is to
It is an object of the present invention to provide a processing method for producing a lithographic printing plate which can be developed with a highly safe developing solution and has sufficient image strength (printing durability and chemical resistance).

[0006]

Means for Solving the Problems As a result of intensive studies conducted by the present inventors in order to achieve the above-mentioned object, the developing property and the strength of the photosensitive layer are made compatible by setting the pH of the developing solution within an appropriate range. The present invention has been completed by discovering that it can be done. That is, the present invention contains at least one compound selected from silicic acid, phosphoric acid, carbonic acid, boric acid, phenols, sugars, oximes and fluorinated alcohols, and has a pH in the range of higher than 12.0 and lower than 13.0. A method for developing a photosensitive lithographic printing plate, which comprises developing with a certain alkaline aqueous solution.

The developer for the photosensitive lithographic printing plate (hereinafter referred to as PS plate) used in the present invention will be described in detail below.

[0008]

[Developer]

[Alkaline agent] The main component of the developer and replenisher used in the processing method of the present invention is at least one compound selected from silicic acid, phosphoric acid, carbonic acid, boric acid, phenols, sugars, oximes and fluorinated alcohols. Contains, pH
Is more than 12.0 and less than 13.0. Among these, weakly acidic substances such as phenols, sugars, oximes and fluorinated alcohols are preferably those having a dissociation index (pKa) of 10.0 to 13.2. Such acids include Pergam
ONION CON CON issued by onPress
STANTS OF ORGANIC ACIDS I
It is selected from those listed in NAQUEOUS SOLUTION and the like. Specifically, salicylic acid (1
3.0), 3-hydroxy-2-naphthoic acid (see 12.
84), catechol (12.6), gallic acid (1)
2.4), sulfosalicylic acid (11.7), 3,4-
Dihydroxysulfonic acid (12.2), 3,4-dihydroxybenzoic acid (11.94), 1,2,4-trihydroxybenzene (11.82), hydroquinone (11.56), pyrogallol ( 11:34), o
-Cresol (10.33), resorsonol (1)
Phenols having a phenolic hydroxyl group such as 1.27), p-cresol (the same 10.27), m-cresol (the same 10.09) and the like.

As the saccharide, a non-reducing sugar which is stable even in alkali is preferably used. Such a non-reducing sugar is a saccharide that does not have a free aldehyde group or a ketone group and does not exhibit reducing properties, and is a trehalose-type oligosaccharide in which reducing groups are bound to each other, or a glycoside in which a reducing group of a saccharide and a non-saccharide are bound to each other. It is classified into sugar alcohols obtained by hydrogenating the body and saccharides, and any of them is preferably used in the present invention. Trehalose-type oligosaccharides include saccharose and trehalose, and examples of glycosides include alkyl glycosides, phenol glycosides, and mustard oil glycosides. As sugar alcohols, D and L
-Arabit, rebit, xylit, D, L-sorbit, D, L-mannite, D, L-idit, D, L
-Talit, Zurisit, Allozulsit and the like. Further, maltitol obtained by hydrogenation of disaccharide and reductant (reduced starch syrup) obtained by hydrogenation of oligosaccharide are preferably used. Furthermore, 2-butanone oxime (12.4) and acetoxime (12.4).
2), 1.2-cycloheptanedione oxime (the same 1
2.3), 2-hydroxybenzaldehyde oxime (12.10), dimethylglyoxime (11.
9), ethanediamide dioxime (11.37), acetophenone oxime (11.35), and other oximes, such as 2,2,3,3-tetrafluoropropanol-1 (12.74), trifluoro. Ethanol (same 12.37), trichloroethanol (same 12.24)
Fluorinated alcohols such as In addition, pyridine-2-aldehyde (same as 1.68), pyridine-
Aldehydes such as 4-aldehyde (12.5)
Adenosine (12.56 ibid.), Inosine (12.56 ibid.)
5), guanine (12.3) and cytosine (12.3).
2), hypoxanthine (same 12.1), xanthine (same 11.9), and other nucleic acid-related substances, as well as diethylaminomethylsulfonic acid (same 12.32.), 1-amino-3,
3,3-trifluorobenzoic acid (same 12.29), isopropylidenedisulfonic acid (same 12.10), 1,1-
Ethylidenediphosphonic acid (11.54), 1,1-ethylidenedisulfonic acid 1-hydroxy (11.5)
2), benzimidazole (12.8), thiobenzamide (12.8), picolinethioamide (1)
2.55) and weak acids such as barbituric acid (12.5). These acidic substances may be used alone or in combination of two or more. Among these acidic substances, silicic acid, phosphoric acid, carbonic acid, sulfosalicylic acid, salicylic acid and sugar alcohols of non-reducing sugars and saccharose are preferable, and especially silicic acid, D-sorbit, saccharose and reduced starch syrup have a suitable pH range. It is preferable because it has a buffering effect and is low in cost.

The proportion of these acidic substances in the developing solution is preferably 0.1 to 30% by weight, more preferably 1
-20% by weight. Below this range, a sufficient buffering effect cannot be obtained, and at concentrations above this range, it is difficult to achieve high concentration, and there is a problem of cost increase. As the base to be combined with these acids, sodium hydroxide, ammonium hydroxide, potassium hydroxide and lithium hydroxide are preferably used. These alkali agents are used alone or in combination of two or more. The above-mentioned various alkaline agents are used by adjusting the pH to a range higher than 12.0 and less than 13 depending on the concentration and combination. A more preferable pH range is 12.1 or more and 12.7 or less. The pH of the developer is 1
When it is 2.0 or less, the image area of the printing plate obtained from such a photosensitive lithographic printing plate that can be developed with a developing solution is physically fragile and wears quickly during printing to obtain sufficient printing durability. I can't. Further, the image area is also chemically weak, and the image of the area wiped with an ink cleaning solvent or a plate cleaner is damaged during printing, and as a result, sufficient chemical resistance cannot be obtained. A high pH developer having a pH of more than 13.0 has strong irritation when it adheres to the skin and mucous membranes, and requires careful handling, which is not preferable.

The combination of the above-mentioned acidic substance and base is, for example, potassium silicate, sodium silicate, lithium silicate,
Ammonium silicate, potassium metasilicate, sodium metasilicate, lithium metasilicate, ammonium metasilicate, tripotassium phosphate, trisodium phosphate, trilithium phosphate, triammonium phosphate, dipotassium phosphate, disodium phosphate,
Dilithium phosphate, diammonium phosphate, potassium carbonate,
Even if added in the form of preformed salts such as sodium carbonate, lithium carbonate, ammonium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, lithium hydrogen carbonate, ammonium hydrogen carbonate, potassium borate, sodium borate, lithium borate, ammonium borate, etc. Good. Also in this case, sodium hydroxide, ammonium, potassium and lithium can be added for pH adjustment. Further, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine,
An organic alkaline agent such as ethyleneimine, ethylenediamine or pyridine may also be used in combination.

The developing solution referred to in the present invention is not only an unused solution used at the start of development, but also a replenishing solution is replenished in order to correct the activity of the solution which is lowered by the processing of the PS plate. Includes a liquid that maintains activity (so-called running liquid). Therefore, since the replenisher needs to have higher activity (alkali concentration) than the developer, the pH of the replenisher is 13.
It may exceed 0.

[0013]

[Surfactant] The developer and replenisher used in the present invention may contain various surfactants and organic compounds as necessary for the purpose of promoting the developability, dispersing the development residue and enhancing the ink affinity of the printing plate image area. A solvent can be added. Preferred surfactants include anionic, cationic, nonionic and amphoteric surfactants. Preferred examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene polystyryl phenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, glycerin fatty acid partial esters, sorbitan. Fatty acid partial ester, pentaerythritol fatty acid partial ester, propylene glycol monofatty acid ester, sucrose fatty acid partial ester, polyoxyethylene sorbitan fatty acid partial ester, polyoxyethylene sorbitol fatty acid partial ester, polyethylene glycol fatty acid ester, poly Glycerin fatty acid partial esters, polyoxyethylenated castor oil, polyoxyethylene glycerin fatty acid partial esters, polio Shiechiren - polyoxypropylene block copolymer, polyoxyethylene ethylenediamine - polyoxypropylene block copolymer adducts, fatty acid diethanolamides, N, N-bis-2-hydroxyalkylamines,
Nonionic surfactants such as polyoxyethylene alkylamine, triethanolamine fatty acid ester, trialkylamine oxide, fatty acid salts, abietic acid salts, hydroxyalkane sulfonic acid salts, alkane sulfonic acid salts, dialkylsulfosuccinic acid ester salts, Straight-chain alkylbenzene sulfonates, branched-chain alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl diphenyl ether sulfonates, alkylphenoxy polyoxyethylene propyl sulfonates, polyoxyethylene alkyl sulfophenyl ether salts, N-methyl-N -Oleyl taurine sodium salt, N-alkylsulfosuccinic acid monoamide disodium salt, petroleum sulfonates, sulfated tallow oil, fatty acid alkyl ester Acid ester salts, alkyl sulfate ester salts, polyoxyethylene alkyl ether sulfuric ester salts, fatty acid monoglyceride sulfate ester salts,
Polyoxyethylene alkyl phenyl ether sulfates, polyoxyethylene styryl phenyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates, styrene / anhydrous Anionic surfactants such as partially saponified maleic acid copolymers, partially saponified olefin / maleic anhydride copolymers, naphthalenesulfonate formalin condensates, alkylamine salts,
Quaternary ammonium salts such as tetrabutylammonium bromide, cationic surfactants such as polyoxyethylene alkylamine salts, polyethylenepolyamine derivatives, carboxybetaines, aminocarboxylic acids, sulfobetaines, aminosulfates, imidazolines, etc. Amphoteric surfactants. Among the above-mentioned surfactants, the term "polyoxyethylene" can be replaced with polyoxyalkylenes such as polyoxymethylene, polyoxypropylene and polyoxybutylene, and these surfactants are also included. A more preferable surfactant is a fluorinated surfactant containing a perfluoroalkyl group in the molecule. As such a fluorine-based surfactant, a perfluoroalkylcarboxylic acid salt,
Anion type such as perfluoroalkyl sulfonate, perfluoroalkyl phosphate ester, amphoteric type such as perfluoroalkyl betaine, cation type such as perfluoroalkyltrimethylammonium salt and perfluoroalkylamine oxide, perfluoroalkylethylene oxide adduct , Perfluoroalkyl group and hydrophilic group-containing oligomer, perfluoroalkyl group and lipophilic group-containing oligomer, perfluoroalkyl group, hydrophilic group and lipophilic group-containing oligomer, perfluoroalkyl group and lipophilic group-containing urethane, etc. A nonionic type is mentioned. The above-mentioned surfactants can be used alone or in combination of two or more kinds, and 0.001 to 10% by weight, more preferably 0.01 to 10% by weight in the developer.
-5% by weight.

[0014]

[Development Stabilizer] In the developer and replenisher used in the present invention, various development stabilizers are preferably used. Preferred examples thereof include polyethylene glycol adducts of sugar alcohols described in JP-A-6-282079, tetraalkylammonium salts such as tetrabutylammonium hydroxide, phosphonium salts such as tetrabutylphosphonium bromide, and iodonium such as diphenyliodonium chloride. Salts are mentioned as preferred examples. Furthermore, an anionic surfactant or an amphoteric surfactant described in JP-A-50-51324,
Further, there are water-soluble cationic polymers described in JP-A-55-95946 and water-soluble amphoteric polymer electrolytes described in JP-A-56-142528. Furthermore,
Organic boron compounds to which alkylene glycol is added, as disclosed in JP-A-59-84241, JP-A-60-1112.
No. 46, polyoxyethylene / polyoxypropylene block polymerization type water-soluble surfactant, JP-A-60-
No. 129750, polyoxyethylene / polyoxypropylene substituted alkylenediamine compound, weight average molecular weight 3 described in JP-A-61-215554.
Polyethylene glycol of 00 or more, JP-A-63-17
Fluorine-containing surfactant having a cationic group described in JP-A-5858, water-soluble ethylene oxide addition compound obtained by adding 4 mol or more of ethylene oxide to acid or alcohol described in JP-A-2-39157, and water-soluble polyalkylene compound And so on.

[0015]

[Organic solvent] If necessary, an organic solvent may be added to the developing solution and the developing replenishing solution. As such an organic solvent, those having a solubility in water of about 10% by weight or less are suitable, and preferably selected from those having a solubility of 5% by weight or less. For example, 1-phenylethanol, 2-phenylethanol, 3-phenyl-1-propanol, 4-phenyl-
1-butanol, 4-phenyl-2-butanol, 2-
Phenyl-1-butanol, 2-phenoxyethanol, 2-benzyloxyethanol, o-methoxybenzyl alcohol, m-methoxybenzyl alcohol, p
-Methoxybenzyl alcohol, benzyl alcohol,
Cyclohexanol, 2-methylcyclohexanol,
3-methylcyclohexanol and 4-methylcyclohexanol, N-phenylethanolamine and N
-Phenyldiethanolamine and the like can be mentioned. The content of organic solvent is 0.1 based on the total weight of the liquid used.
It is preferably up to 5% by weight, but substantially not contained, and particularly preferably not contained at all. Here, “not substantially contained” means 1% by weight or less.

[0016]

[Reducing agent] A reducing agent is added to the developing solution and the replenishing solution used in the present invention, if necessary. This prevents stains on the printing plate and is particularly effective when developing a negative photosensitive lithographic printing plate containing a photosensitive diazonium salt compound. As a preferable organic reducing agent, thiosalicylic acid,
Examples thereof include phenol compounds such as hydroquinone, methol, methoxyquinone, resorcin, and 2-methylresorcin, and amine compounds such as phenylenediamine and phenylhydrazine. More preferable inorganic reducing agents include sodium salts, potassium salts, and ammonium salts of inorganic acids such as sulfurous acid, bisulfite, phosphorous acid, phosphite, dihydrogen phosphite, thiosulfate and dithionite. Examples thereof include salt. Among these reducing agents, sulfites are particularly excellent in the stain prevention effect. These reducing agents are preferably used in a developing solution at the time of use.
It is contained in the range of 0.5 to 5% by weight.

[0017]

[Organic Carboxylic Acid] If necessary, an organic carboxylic acid may be added to the developer and replenisher used in the present invention. Preferred organic carboxylic acid has 6 to 2 carbon atoms.
0 aliphatic and aromatic carboxylic acids.
Specific examples of the aliphatic carboxylic acid include caproic acid,
There are enanthic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid and the like, and particularly preferred are alkanoic acids having 8 to 12 carbon atoms. Further, it may be an unsaturated fatty acid having a double bond in the carbon chain or a branched carbon chain. The aromatic carboxylic acid is a compound in which a benzene ring, a naphthalene ring, an anthracene ring or the like is substituted with a carboxyl group, and specifically, o-
Chlorobenzoic acid, p-chlorobenzoic acid, o-hydroxybenzoic acid, p-hydroxybenzoic 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-
Although there are naphthoic acid and the like, hydroxynaphthoic acid is particularly effective. The above aliphatic and aromatic carboxylic acids are preferably used as a sodium salt, a potassium salt or an ammonium salt in order to enhance water solubility. The content of the organic carboxylic acid in the developer used in the present invention is not particularly limited,
If it is less than 0.1% by weight, the effect is not sufficient, and if it is 10% by weight or more, not only the effect cannot be further improved but also dissolution may be hindered when another additive is used in combination. Therefore, the preferable addition amount is 0.1 to 10% by weight with respect to the developing solution at the time of use, and more preferably 0.5 to
It is 4% by weight.

[0018]

[Others] In addition to the above additives, the following additives may be added to the developer and replenisher used in the invention. For example, JP-A-58-75152
Neutral salts such as NaCl, KCl and KBr described in JP-A-59-121336 and [Co (N
H _{3)] 6} Cl _3, etc. complexes, JP 56-142258
Ampholytic polyelectrolytes such as copolymers of vinylbenzyltrimethylammonium chloride and sodium acrylate described in JP-A-59-75255.
Organic metal surfactants containing i, Ti, etc., JP-A-59-8
Examples thereof include organic boron compounds described in Japanese Patent No. 4241.
The developer and replenisher used in the present invention may further contain a preservative, a colorant, a thickener, a defoaming agent, a water softener and the like, if necessary. Examples of the defoaming agent include mineral oils, vegetable oils, alcohols, surfactants, silicones and the like described in JP-A-2-244143. Examples of the water softener include polyphosphoric acid and its sodium salt, potassium salt and ammonium salt, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, hydroxyethylethylenediaminetriacetic acid, nitrilotriacetic acid,
1,2-diaminocyclohexanetetraacetic acid and 1,
Aminopolycarboxylic acids such as 3-diamino-2-propanoltetraacetic acid and their sodium, potassium and ammonium salts, aminotri (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), Triethylenetetramine hexa (methylenephosphonic acid), hydroxyethylethylenediamine tri (methylenephosphonic acid) and 1-hydroxyethane-1,1
Mention may be made of diphosphonic acids and their sodium, potassium and ammonium salts. The optimum value of such a water softener varies depending on its chelating power, the hardness of hard water used, and the amount of hard water. %, More preferably 0.01 to 0.5% by weight. If the addition amount is less than this range, the intended purpose is not sufficiently achieved, and if the addition amount is more than this range, the image area is adversely affected such as color loss. The remaining component of the developer and replenisher is water.

[0019]

[Concentrated liquid] The developer and replenisher used in the present invention are concentrated liquids containing less water than in use,
It is advantageous in transportation to dilute with water before use. In this case, the degree of concentration is appropriate to the extent that each component does not separate or precipitate, but it is preferable to add a solubilizing agent if necessary. As such a solubilizing agent, Japanese Patent Laid-Open No.
So-called hydrotropes such as toluene sulfonic acid, xylene sulfonic acid and their alkali metal salts described in JP-A-32081 are preferably used.

[0020]

[Development treatment] In the treatment method of the present invention, the PS plate is exposed through a transparent original image with an actinic ray from a carbon arc lamp, a mercury lamp, a metal halide lamp, a xenon lamp, a tungsten lamp, etc. Used for development processing. In recent years, in the plate making and printing industries, automatic developing machines for PS plates have been widely used in order to streamline and standardize plate making operations. This automatic developing machine is generally composed of a developing section and a post-processing section, and is composed of a device for conveying PS plates, each processing liquid tank and a spraying device, and while conveying the exposed PS plates horizontally, it is pumped up by a pump. Each processing solution is sprayed from a spray nozzle for development and post-processing. Further, recently, a method of developing a PS plate by immersing and transporting the PS plate in a developing tank filled with a developing solution by means of a submerged guide roll or the like has been developed, and such a developing method can also be suitably applied to the present invention. . In such an automatic processor, processing can be performed while replenishing the replenisher according to the development processing amount, operating time, and the like. Especially PS
It is also preferable to use a method of detecting the activity of the liquid, which is decreased by the plate treatment, by the conductivity or impedance, and feeding back the result to replenish the replenishing liquid to keep the activity constant. Further, a so-called disposable developing method in which processing is performed with a substantially unused developing solution can be applied.

[0021]

[Post-treatment] The PS plate developed with the developer having such a composition is post-treated with washing water, a rinse solution containing a surfactant, a finisher or a protective gum solution mainly containing gum arabic or a starch derivative. Is given. Various combinations of these treatments can be used in the post-treatment of the PS plate of the present invention. For example, after development → washing → rinsing solution containing a surfactant or development → washing → finisher solution The finisher liquid is less fatigued, which is preferable.
Further, a countercurrent multi-stage treatment using a rinse liquid or a finisher liquid is also a preferable embodiment. These post-treatments are generally performed using an automatic developing machine including a developing section and a post-processing section.
As the post-treatment liquid, a method of spraying from a spray nozzle or a method of carrying it by dipping in a treatment tank filled with the treatment liquid is used. Further, a method is also known in which after development, a small amount of washing water of a certain amount is supplied to the plate surface to wash it, and the waste solution thereof is reused as dilution water for the developing solution stock solution. In such automatic processing, each processing solution can be processed while being replenished with each replenishing solution according to the processing amount, operating time, and the like. Further, a so-called disposable treatment method of treating with a substantially unused post-treatment liquid can be applied. The planographic printing plate obtained by such processing is set on an offset printing machine and used for printing a large number of sheets.

[Support] The support for the photosensitive lithographic printing plate used in the present invention is described below. The support material is preferably a flexible material that can be set in an ordinary lithographic printing plate and one that can withstand a load applied during printing, and for example, a metal plate such as aluminum, magnesium, zinc, chromium, iron, copper, nickel, or a metal thereof. Alloy plates, etc.
Further, a plate-like body made of a metal plate or a polymer material coated with chromium, zinc, copper, nickel, aluminum, iron or the like through a plating, vapor deposition or spraying or an adhesive layer, a paper or a polymer material. Papers laminated with may be used. Among these, preferred support materials include aluminum and its alloys.

As an aluminum alloy, JIS A1
050, A1100, A3003, A3005, A31
A rolled plate made of an alloy such as 03 material and having a plate thickness of 0.1 to 0.5 mm is generally used. Generally, the surface of the ingot obtained by semi-continuous casting is removed by chamfering, and if necessary, After being subjected to homogenization treatment by hot rolling, it is heated to a predetermined temperature, hot rolled, then subjected to intermediate annealing in the middle of cold rolling, and then subjected to final cold rolling. Further, such an aluminum rolled plate is manufactured by continuously casting and rolling an aluminum alloy coil having a plate thickness of 20 mm or less from a molten aluminum, and then performing cold rolling, heat treatment, straightening, etc. without homogenizing treatment. What was done can also be used. Prior to roughening the aluminum plate, if necessary, a degreasing treatment for removing rolling oil on the surface may be performed with, for example, a surfactant, an organic solvent, or an alkaline aqueous solution. In the case of alkali, a treatment such as neutralization with an acidic solution and removal of smut may be performed next.

Next, in order to improve the adhesion between the support and the photosensitive layer and impart water retention to the non-image area, a so-called graining treatment is carried out to roughen the surface of the support. Specific means of this graining method include sand blasting, ball grain, wire grain, brush grain with nylon brush and abrasive / water slurry,
There is a mechanical graining method such as honing grain which sprays abrasive / water slurry onto the surface at high pressure, and there is also a chemical graining method where the surface is roughened with an etching agent consisting of alkali or acid or a mixture thereof. . Also, British Patent No. 896,563 and JP-A-5
3-67507, JP-A-54-146234 and JP-B-48-28123, or an electrochemical graining method, or JP-A-53-1232.
No. 04, JP-A-54-63902, a method combining a mechanical graining method and an electrochemical graining method, and a mechanical method described in JP-A-56-55261. It is also known to combine a graining method and a chemical graining method with a saturated aqueous solution of an aluminum salt of a mineral acid. Further, to the support material, a method of adhering a granular material with an adhesive or a method having its effect to roughen the surface, or a continuous band or roll having fine unevenness is pressure-bonded to the support material to form unevenness. A rough surface may be formed by transferring. A plurality of such surface roughening methods may be performed in combination, and the order, the number of repetitions, etc. can be arbitrarily selected. When a plurality of surface-roughening treatments are combined, chemical treatment with an acid or alkali aqueous solution can be performed during that time so that the subsequent surface-roughening treatment can be performed uniformly.

Specific examples of the above acid or alkali aqueous solution include, for example, hydrofluoric acid, fluorozirconic acid, phosphoric acid, sulfuric acid,
Examples thereof include acids such as hydrochloric acid and nitric acid, and alkaline aqueous solutions such as sodium hydroxide, sodium silicate, and sodium carbonate. These acid or alkali aqueous solutions may be used alone or in combination of two or more. The chemical treatment is 0.05-40 of these acids or alkalis.
It is common to perform treatment for 5 to 300 seconds at a liquid temperature of 40 ° C. to 100 ° C. using a weight% aqueous solution. Since smut is generated on the surface of the support obtained by the above-mentioned roughening treatment, that is, graining treatment, appropriate treatment such as washing with water or alkali etching should be performed to remove this smut. Are generally preferred. As such a treatment, for example, the alkaline etching method described in Japanese Patent Publication No. 48-123123 or Japanese Patent Laid-Open No. 53-12 is used.
Examples thereof include a treatment method such as a sulfuric acid desmutting method described in Japanese Patent No. 739. In the case of the aluminum support used in the present invention, after the pretreatment as described above, usually, in order to improve wear resistance, chemical resistance, water retention,
An oxide film is formed on the support by anodic oxidation.

As the electrolyte used for the anodizing treatment of the aluminum plate, any electrolyte can be used as long as it forms a porous oxide film, and generally, sulfuric acid,
Phosphoric acid, oxalic acid, chromic acid or a mixed acid thereof is used. The concentration of these electrolytes is appropriately determined depending on the type of electrolyte. The treatment conditions for anodic oxidation cannot be unconditionally specified because they vary depending on the electrolyte used, but generally the concentration of the electrolyte is 1 to 80% solution, the liquid temperature is 5 to 70 ° C, and the current density is 5 to 60 A / dm ^2. , Voltage 1 to 100 V, electrolysis time 10
It is appropriate to be in the range of seconds to 5 minutes. The amount of the anodized film is suitably 1.0 g / m ² or more, but more preferably in the range of 2.0 to 6.0 g / m ^2. If the anodized film is less than 1.0 g / m ² , printing durability may be insufficient,
The non-image area of the planographic printing plate is easily scratched, and so-called "scratch stain" in which ink adheres to the scratched portion during printing is likely to occur. Although such anodizing treatment is performed on a surface used for printing of the support of the lithographic printing plate, the back around the electric lines of force, the anodized film 0.01 to 3 g / m ² on the back surface It is generally formed. Further, it is possible to perform anodizing treatment in an alkaline aqueous solution (for example, several% caustic soda aqueous solution) or molten salt, or for example, anodizing treatment for forming a non-porous anodized film using an ammonium borate aqueous solution. . Prior to the anodizing treatment, JP-A-4-1-1
The hydrated oxide film formation described in JP-A-48991 and JP-A-4-97896 may be carried out.
-56497 and treatment in a metal silicate solution described in JP-A-63-67295, hydrated oxide film formation treatment, and chemical conversion film formation treatment described in JP-A-56-144195. You can also do

The aluminum support of the present invention can be used after the anodizing treatment by treatment with an organic acid or a salt thereof, or as an undercoat layer for coating the photosensitive layer. Examples of the organic acid or its salt include organic carboxylic acid, organic phosphonic acid, organic sulfonic acid and its salt, and the like, and organic carboxylic acid or its salt is preferable. Examples of the organic carboxylic acids include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, lauric acid, palmitic acid and stearic acid; unsaturated aliphatic monocarboxylic acids such as oleic acid and linoleic acid; oxalic acid and succinic acid. Aliphatic dicarboxylic acids such as adipic acid and maleic acid; oxycarboxylic acids such as lactic acid, gluconic acid, malic acid, tartaric acid and citric acid; aromatic carboxylic acids such as benzoic acid, mandelic acid, salicylic acid and phthalic acid, and Ia, IIb, IIIb, IVa, VIb and VIII
Group metal salts and ammonium salts are mentioned. Of the above organic carboxylic acid salts, preferred are formic acid, acetic acid, butyric acid,
The above-mentioned metal salts and ammonium salts of propionic acid, lauric acid, oleic acid, succinic acid and benzoic acid.
You may use these compounds individually or in combination of 2 or more types. These compounds are 0.001 in water and alcohol.
It is preferably dissolved to a concentration of 10 to 10% by weight, particularly 0.01 to 1.0% by weight, and the treatment condition is 25
To 95 ° C., preferably 50 to 95 ° C., pH is 1 to 13, preferably 2 to 10, 10 seconds to 20 minutes, preferably 10 seconds to 3 minutes, or the support is immersed in the treatment liquid. Apply to the body.

Further, after the anodizing treatment, the following treatment with a compound solution or these compounds can be used as an undercoat layer for coating a photosensitive layer. glycine,
Amino acids such as alanine, valine, serine, threonine, aspartic acid, glutamic acid, arginine, lysine, tryptophan, parahydroxyphenylglycine, dihydroxyethylglycine and anthranilic acid; aliphatic aminosulfonic acids such as sulfamic acid and cyclohexylsulfamic acid; 1- Aminomethylphosphonic acid, 1-dimethylaminoethylphosphonic acid, 2-aminoethylphosphonic acid, 2-aminopropylphosphonic acid, 4-aminophenylphosphonic acid, 1-aminoethane-1,1-diphosphonic acid, 1-amino-1- Phosphonic acids such as phenylmethane-1,1-diphosphonic acid, 1-dimethylaminoethane-1,1-diphosphonic acid, 1-dimethylaminobutane-1,1-diphosphonic acid and ethylenediaminetetramethylenephosphonic acid Compound or hydrochloric acid, such as phosphinic acid for changing the phosphonic acid phosphinic acid group, sulfuric acid, nitric acid,
Sulfonic acid (methanesulfonic acid, etc.), formic acid, oxalic acid, alkali metal, ammonia, lower alkanolamine (triethanolamine, etc.), lower alkylamine (triethylamine, etc.) salts, polyacrylic acid, polyacrylamide, polyvinyl alcohol, poly Acrylic acid copolymers such as hydroxyethyl acrylate and polyvinyl pyrrolidone; Malein copolymers such as polyethylene imine, diacryl dimethyl aluminum chloride, polyvinyl imidazoline and polyalkylaminoethyl acrylate;
Polyethylene glycol polyoxyethylene, polypropylene glycol, ethylenediamine, hexaethylenediamine, polyurethane resin, polyhydroxymethylurea, polyhydroxymethylmelamine resin, soluble starch, CMC (carboxymethyl cellulose), hydroxyethyl cellulose, guar gum, tragacanth gum, xanthan gum, sodium alginate. , Gelatin, PVPA (polyvinylphosphonic acid), optionally substituted phenylphosphonic acid, naphthylphosphonic acid, alkylphosphonic acid, glycerophosphonic acid, methylenediphosphonic acid, and organic phosphonic acids such as ethylenediphosphonic acid, Organic phosphoric acid such as phenyl phosphoric acid, naphthyl phosphoric acid, alkyl phosphoric acid and glycerophosphoric acid, which may have a substituent, substituted Phenyl phosphinic acid which may have a, naphthyl phosphinic acid, organic phosphinic acids such as alkyl phosphinic acid and glycero phosphinic acid,
It is selected from amino acids such as glycine and β-alanine, and hydrochlorides of amines having a hydroxyl group such as triethanolamine hydrochloride, but two or more thereof may be mixed and used.

Further, 3 ', 5,7-trihydroxy-
4'-methoxyflavone-7-rutinopyranoside,
(+) Rutin trihydrate, salicin, phenyl-
β-p-glucopyranoside, narizine hydrate, hespyridine, hespyridine methyl chalcone, glycyl lysic acid monoammonium salt hydrate,
18-β Glycyl Retec Acid, Esculin Monohydrate, Saponin, Alkyl Glucoxide (C ₈
~ C ₁₆ ) and the like, sorbitol, gluconic acid, pentaacetyl glucose, maltose, sucrose, glucose, saccharose, arabinose, galactose, rhamnose, mannose, fructose, reduced starch syrup, acacia gum, trancant gum, dextrin,
Sugars such as soluble starch and agar, and polyhydric alcohols such as ethylene glycol, glycerin and D-sorbit are also used. The above compounds may be used alone or in combination of two or more kinds. In the case of treatment, these compounds are preferably dissolved in water or alcohol to a concentration of 0.001 to 10% by weight, particularly 0.01 to 1.0% by weight, and the treatment condition is 25 to 95 ° C. The support is immersed in a temperature range of preferably 50 to 95 ° C. and a pH of 1 to 13, preferably 2 to 10 for 10 seconds to 20 minutes, preferably 10 seconds to 3 minutes.

When it is used as an undercoat layer for coating a photosensitive layer, it is similarly added to water or alcohol in an amount of 0.001 to 10% by weight,
In particular, it is dissolved so as to have a concentration of 0.01 to 1.0% by weight, and if necessary, the pH is adjusted with a basic substance such as ammonia, triethylamine and potassium hydroxide, or an acidic substance such as hydrochloric acid and phosphoric acid. However, it can also be used in the range of pH 1-12. Further, a yellow dye may be added to improve the tone reproducibility of the photosensitive lithographic printing plate.
Coverage of the organic undercoat layer after drying, 2 to 200 mg / m ² are suitable, and preferably from 5 to 100 mg / m ^2. If the coating amount is less than 2 mg / m ² , sufficient effects cannot be obtained for the original purpose such as preventing stains. If it exceeds 200 mg / m ² , the printing durability will be reduced.

An intermediate layer may be provided to enhance the adhesion between the support and the photosensitive layer. To improve the adhesion,
Generally, the intermediate layer is made of a diazo resin, a phosphoric acid compound that is adsorbed on aluminum, or the like. The thickness of the intermediate layer is arbitrary, and must be a thickness capable of performing a uniform bond-forming reaction with the upper photosensitive layer upon exposure. Normal,
A dry solid coating rate of about 1 to 100 mg / m ² is good.
40 mg / m ² is particularly good. The proportion of the diazo resin used in the intermediate layer is 30 to 100%, preferably 60 to
It is 100%.

Prior to the above-mentioned treatment and application of the undercoat layer, the anodized support is washed with water, and then the dissolution of the anodized film in the developing solution is suppressed and the residual film of the photosensitive layer component is suppressed. The following treatments can be performed for the purpose of improving the strength of the anodized film, improving the hydrophilicity of the anodized film, and improving the adhesion to the photosensitive layer. One of them is a silicate treatment in which the anodic oxide film is treated by contact with an aqueous solution of an alkali metal silicate. In this case, the concentration of the alkali metal silicate is 0.1 to 30% by weight, preferably 0.5 to 15% by weight, and the pH at 25 ° C is 10 to 1%.
5 to 80 ° C., preferably 10 to 7 in an aqueous solution of 3.5
Contact at 0 ° C., more preferably 15 to 50 ° C. for 0.5 to 120 seconds. The contacting method may be dipping or spraying, or any method. If the pH of the alkali metal silicate aqueous solution is lower than 10, the liquid gels, and if it is higher than 13.5, the anodic oxide film is dissolved. As the alkali metal silicate used in the present invention, sodium silicate, potassium silicate, lithium silicate and the like are used. The hydroxide used for adjusting the pH of the alkali metal silicate aqueous solution includes sodium hydroxide, potassium hydroxide, lithium hydroxide and the like. The treatment liquid may contain an alkaline earth metal salt or a Group IVB metal salt. Alkaline earth metal salts include nitrates such as calcium nitrate, strontium nitrate, magnesium nitrate, and barium nitrate, and water-soluble salts such as sulfates, hydrochlorides, phosphates, acetates, oxalates, and oxalates. Examples include salt. Examples of the Group IVB metal salt include titanium tetrachloride, titanium trichloride, potassium titanium fluoride, titanium potassium oxalate, titanium sulfate, titanium tetraiodide, zirconium chloride oxide and the like. Alkaline earth metal or
Group IVB metal salts may be used alone or in combination of two or more. The preferred range of these metal salts is 0.
01 to 10% by weight, more preferably 0.05 to
5.0% by weight.

In addition, various sealing treatments can be given, which are commonly used.
Known as a method for sealing the anodized film,
Steam sealing, boiling water (hot water) sealing, metal salt sealing (chromic acid)
Salt / dichromate sealing, nickel acetate sealing, etc.), fats and oils
Impregnation sealing, synthetic resin sealing, low temperature sealing (red blood salt or alkali
It is possible to use a printing plate
Performance as a support (adhesion and hydrophilicity with the photosensitive layer),
From the viewpoint of high-speed processing, low cost, low pollution, etc.
Relatively preferred. As the method, for example, Japanese Patent Laid-Open No.
Pressurization or constant pressure disclosed in Japanese Patent Publication No. 176690.
Pressure water vapor continuously or discontinuously, relative humidity 70% or more
・ Anodic oxidation for 2 seconds to 180 seconds at steam temperature of 95 ℃ or higher
Examples include a method of contacting the film. Other sealing treatment
As the method, the support is heated with hot water of about 80 to 100 ° C. or
A method of dipping or spraying in an alkaline aqueous solution,
Alternatively or subsequently, dip in a nitrous acid solution or
Can be spray treated. As an example of nitrite
Is Ia, IIa, IIb, IIIb, IVb, IVa, VI of the periodic table.
a, VIIa, VIII metal nitrite or ammonium
Salt, that is, ammonium nitrite, its metal
Examples of the salt include LiO₂, NaNO₂, KNO ₂,
Mg (NO₂)₂, Ca (NO₂)₂, Zn (NO_Three)
₂, Al (NO₂) _Three, Zr (NO₂)_Four, Sn (NO
₂)_Three, Cr (NO₂)_Three, Co (NO₂) ₂, Mn
(NO₂)₂, Ni (NO₂)₂Are preferred, and
Lucari metal nitrate is preferred. Use two or more nitrites together
You can also.

The treatment conditions cannot be uniquely determined because they differ depending on the state of the support and the type of alkali metal, but
For example, when sodium nitrite is used, the concentration is generally 0.001-10% by weight, more preferably 0.0
1-2% by weight, bath temperature generally from room temperature to about 100 ° C
Before and after, more preferably 60 to 90 ° C., the treatment time may be generally selected from the range of 15 to 300 seconds, more preferably 10 to 180 seconds. P of nitrous acid aqueous solution
H is preferably adjusted to 8.0 to 11.0, and particularly preferably adjusted to 8.5 to 9.5. To adjust the pH of the nitrous acid aqueous solution to the above range,
For example, it can be suitably prepared using an alkaline buffer or the like. Examples of the alkaline buffer include, but are not limited to, a mixed aqueous solution of sodium hydrogen carbonate and sodium hydroxide, a mixed aqueous solution of sodium carbonate and sodium hydroxide, a mixed aqueous solution of sodium carbonate and sodium hydrogen carbonate, and sodium chloride and sodium hydroxide. Mixed aqueous solution,
A mixed aqueous solution of hydrochloric acid and sodium carbonate, a mixed aqueous solution of sodium tetraborate and sodium hydroxide, and the like can be preferably used. In addition, an alkali metal salt other than sodium, such as potassium salt, can be used as the above alkaline buffer solution. After performing the silicate treatment or the pore-sealing treatment as described above, the acidic aqueous solution treatment and the hydrophilic undercoating disclosed in JP-A-5-278362 may be performed in order to improve the adhesion to the photosensitive layer. Japanese Patent Laid-Open No. 4-2
The organic layer disclosed in Japanese Patent Application No. 82637 or Japanese Patent Application No. 6-108678 may be provided.

After the surface of the support is subjected to the above-mentioned treatment or undercoating, a back coat is provided on the back surface of the support, if necessary. As such a back coat, a coating layer composed of a metal oxide obtained by hydrolyzing and polycondensing an organic polymer compound described in JP-A-5-45885 and an organic or inorganic metal compound described in Japanese Patent Application No. 4-189448. Is preferably used. Among these coating layers, Si (OCH ₃ ) ₄ and Si (OC ₂ H
₅ ) ₄ , Si (OC ₃ H ₇ ) ₄ , Si (OC
A silicon alkoxy compound such as ₄ H ₉ ) ₄ is inexpensive and easily available, and a metal oxide coating layer obtained from it is excellent in developing resistance and is particularly preferable.

A preferable characteristic of the support for a lithographic printing plate is a center line average roughness of 0.10 to 1.2 μm, and when it is less than 0.10 μm, the adhesiveness to the photosensitive layer deteriorates.
This causes a marked decrease in printing durability. If it is larger than 1.2 μm, the stain resistance during printing will deteriorate. Further, the color density of the support is 0.15 to 0.
When it is 65 and is whiter than 0.15, halation during image exposure is too strong, which hinders image formation.
When it is blacker than 0.65, the image is difficult to see in the plate inspection work after development and the plate inspection property is remarkably poor.

Next, the photosensitive lithographic printing plate used in the present invention will be described. There are a positive type and a negative type in the photosensitive lithographic printing plate, and the present invention may be either. First, the positive photosensitive lithographic printing plate will be described. This is a positive type photosensitive layer coated on the support.

[0038]

[Photosensitive layer] The photosensitive layer in the present invention contains an alkali-soluble binder resin, and examples of the alkali-soluble resin include phenol formaldehyde resin, cresol formaldehyde resin, phenol cresol mixed formaldehyde resin, p-substituted phenol and phenol or cresol and formaldehyde. Novolak type phenol resin such as co-condensate resin, novolak resin having phenolic hydroxyl group and carboxyl group, salicylic acid-formaldehyde resin, salicylic acid-m-cresol-formaldehyde resin, 4-methylsalicylic acid-formaldehyde resin, 6-propyl Salicylic acid-phenol formaldehyde resin, 4,6-dimethylsalicylic acid-acetaldehyde resin, p-oxybenzoic acid-resorcinol-benzal Hydrin resin, 2-methyl-4-hydroxybenzoic acid - formaldehyde resins, 2,6-dimethyl -
4-oxybenzoic acid-acetaldehyde resin, 2,4-
Dioxybenzoic acid-p-cresol-formaldehyde resin, 2,6-dioxybenzoic acid-butyraldehyde resin, 4-chloro-2,6-dioxybenzoic acid-m-cresol-formaldehyde resin, 4-methoxy-2,6
-Dioxybenzoic acid-formaldehyde resin, gallic acid-formaldehyde resin, gallic acid-resorcinol-formaldehyde resin, phloroglucincarboxylic acid-benzaldehyde resin, phloroglucincarboxylic acid-acetone resin, phloroglucincarboxylic acid-resorcinol-benzophenone resin , 2,4,5-Trioxybenzoic acid-furfural resin, galloyl gallic acid-pyrogallol-p-
Nitrobenzaldehyde resin, tannic acid-resorcinol-aldehyde resin, tannic acid-m-cresol-aldehyde resin, tannic acid-p-oxybenzoic acid-resorcinol-formaldehyde resin, 4,6-dioxyphthalic acid-resorcinol-formaldehyde resin, (2 , 4-dioxyphenyl) acetic acid-propionaldehyde resin,
(3,4,5-trioxyphenyl) acetic acid-m-cresol-formaldehyde resin, pyrogallolacetone resin and the like. There is also a condensation type resin containing a condensation unit of an aromatic compound containing two or more phenolic hydroxyl groups and an aldehyde or a ketone. Some of them will be explained. Examples of aromatic compounds containing two or more phenolic hydroxyl groups are resorcin, 2-methylresorcin, 5-methylresorcin, and 2
-Ethylresorcin, 5-ethylresorcin, 2-propylresorcin, 2-isopropylresorcin, 2-t
-Butylresorcin, 5-t-butylresorcin, 2-
Pentylresorcin, 2-hexylresorcin, 2-octylresorcin, 5-chlorresorcin, 5-methoxyresorcin, 2-methyl-5-chlorresorcin, 2
-Ethyl-5-chlorresorcin, 2,5-dimethylresorcin, 2-methyl-5-ethylresorcin, 2-methyl-5-methoxyresorcin, 2,5-diethylresorcin, 2-t-butyl-methylresorcin, pyrogallol , 5-chloropyrogallol, 5-methoxypyrogallol, 5-methylpyrogallol, 5-ethylpyrogallol and 5-t-butyl-pyrogallol. Further, as the aldehydes or ketones, acetaldehyde, formaldehyde, acetone, methyl ethyl ketone, diethyl ketone, benzaldehyde, 4-methylbenzaldehyde, 4-ethylbenzaldehyde, 4-
Examples are t-butylbenzaldehyde, acetophenone, 4-methylacetophenone, benzophenone, 4-methylbenzophenone and 4,4'-dimethylbenzophenone.

These aromatic compounds containing two or more phenolic hydroxyl groups and aldehydes / ketones can be freely combined with each other, and two or more kinds of them can be mixed and copolycondensed. Copolycondensation with phenol, p-substituted phenol, m-cresol, p-cresol, etc. is also possible. Further, there are phenol-modified xylene resin, polyhydroxystyrene, polyhalogenated hydroxystyrene and the like. Of these, the phenolic resins described below are particularly preferable. That is, it is a novolac type phenol-formaldehyde resin having a content of trinuclear or higher components of 90% by weight or more and a weight average molecular weight of 5000 or more. It is more preferably 10,000 or more. Here, the weight average molecular weight is defined as a value in terms of polystyrene measured by gel permeation chromatography (GPC).

The phenol-formaldehyde resin is synthesized by condensing phenol with aldehydes such as formaldehyde or paraformaldehyde using an acidic catalyst. In particular, in order to obtain a phenol-formaldehyde resin having a weight average molecular weight of 5000 or more, which is used in the present invention, 0.7 to 1 mol of phenol is used.
Preference is given to using 0.9 mol of aldehydes. If the aldehyde content is 0.7 mol or less, a sufficient molecular weight cannot be obtained, and if it exceeds 0.9 mol, a gelled product is likely to be formed, which is not preferable. As the acidic catalyst used in the condensation reaction, hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid, and the like can be used, and oxalic acid is preferable.

When the phenol / formaldehyde resin thus obtained contains 10% by weight or more of a component having a binuclear structure or less, a low molecular weight component is removed by a method such as fractional precipitation, fractional dissolution, column chromatography or the like to produce a binuclear body. The following components should be 10% by weight or less. The amount of resin in the total amount of the photosensitive composition of the present invention is 30 to 90% by weight, and more preferably 40 to 70% by weight. In addition, the photosensitive composition of the present invention may optionally contain an alkali-soluble resin other than novolak.
The alkali-soluble film-forming resin having at least one or more selected from the monomer residues shown in (1) to (26) below as a polymerization component is preferable.

(1) N- (4-hydroxyphenyl) acrylamide or N- (4-hydroxyphenyl) methacrylamide, o-, m- or p-hydroxystyrene, o- or m-bromo-p-hydroxystyrene, o- or m-chloro-p-hydroxystyrene,
Acrylamides, methacrylamides, acrylic acid esters, methacrylic acid esters and hydroxystyrenes having an aromatic hydroxyl group such as o-, m- or p-hydroxyphenyl acrylate or methacrylate, (2) acrylic acid, methacrylic acid, Citraconic acid,
(Substituted) unsaturated carboxylic acids such as citraconic anhydride, maleic acid, maleic anhydride and its half ester, itaconic acid, itaconic anhydride and its half ester, (3) N- (o-aminosulfonylphenyl) acrylamide, N -(M-aminosulfonylphenyl) acrylamide, N- (p-aminosulfonylphenyl)
Acrylamide, N- [1- (3-aminosulfonyl)
Naphthyl] acrylamides, acrylamides such as N- (2-aminosulfonylethyl) acrylamide, N
-(O-aminosulfonylphenyl) methacrylamide, N- (m-aminosulfonylphenyl) methacrylamide, N- (p-aminosulfonylphenyl) methacrylamide, N- [1- (3-aminosulfonyl) naphthyl] methacrylamide , Methacrylamides such as N- (2-aminosulfonylethyl) methacrylamide,
Also, o-aminosulfonylphenyl acrylate, m
-Unsaturated sulfonamides such as acrylic acid esters such as -aminosulfonylphenyl acrylate, p-aminosulfonylphenyl acrylate, 1- (3-aminosulfonylphenylnaphthyl) acrylate, o-aminosulfonylphenyl methacrylate, m-aminosulfonylphenyl methacrylate , P-aminosulfonylphenylmethacrylate, unsaturated sulfonamides such as methacrylic acid esters such as 1- (3-aminosulfonylphenylnaphthyl) methacrylate, and (4) phenyl which may have a substituent such as tosylacrylamide. Sulfonylacrylamide, and phenylsulfonylmethacrylamide that may have a substituent such as tosylmethacrylamide, and maleimide (5) acrylic having an aliphatic hydroxyl group Esters and methacrylic acid esters, for example, 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate, hydroxyalkyl acrylate (number-alkyl C ₃ -C _10), hydroxyalkyl methacrylates _{(C 3 ~C 10) (6} ) acrylic acid Methyl, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, cyclohexyl acrylate, octyl acrylate, phenyl acrylate, benzyl acrylate, 2-chloroethyl acrylate, 4-hydroxy acrylate (Substituted) acrylic acid esters such as butyl, glycidyl acrylate, N-dimethylaminoethyl acrylate, (7) methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacryl Butyl methacrylate, amyl, hexyl methacrylate, cyclohexyl methacrylate, octyl methacrylate, phenyl methacrylate, benzyl methacrylate, -2
-Chloroethyl, 4-hydroxybutyl methacrylate,
(Substituted) methacrylates such as glycidyl methacrylate and N-dimethylaminoethyl methacrylate;
(8) Acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-ethylacrylamide, N-ethylmethacrylamide, N-hexylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide,
N-cyclohexylmethacrylamide, N-hydroxyethylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-phenylmethacrylamide, N-benzylacrylamide, N-benzylmethacrylamide, N-nitrophenylmethacrylamide, N-nitro Phenylmethacrylamide, N-
Acrylamide or methacrylamide such as ethyl-N-phenylacrylamide and N-ethyl-N-phenylmethacrylamide, and acrylanilide;
Vinyl ethers such as p-chloroacrylanilide, m-nitroacrylanilide, m-methoxyacrylanilide (9) ethyl vinyl ether, methyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether and phenyl vinyl ether. , Vinyl chloride, vinylidene chloride, vinylidene cyanide, etc. (10) Vinyl acetates such as vinyl acetate, vinyl chloroacetate, vinyl butyrate, vinyl benzoate, vinyl pyropionate, (1
1) Styrene, α-methylstyrene, methylstyrene,
Styrenes such as chloromethylstyrene, (12) vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone and phenyl vinyl ketone,
(13) Olefins such as ethylene, propylene, isobutylene, butadiene and isoprene, (14) N-vinylpyrrole, N-vinylindole, N-vinylpyrrolidene, N-vinylpyrrolidone, N-vinylcarbazole,
4-vinylpyridine, acrylonitrile, methacrylonitrile, etc. (15) General formula [I]

[0043]

Embedded image

Represents R₁Is a hydrogen atom or a halogen atom
Or represents an alkyl group. R₂, R_ThreeAre independent
Hydrogen atom, halogen atom, alkyl group, substituted alkyl group
Group, aromatic group, substituted aromatic group, -OR_Four, -COOR
_Five, -CONHR ₆, -COR₇, Or -CN
Forget or R₂And R_ThreeMay combine to form a ring
R_Four~ R₇Each represents an alkyl group or an aromatic group.
You. n represents 2 or 3. (16) General formula [II]

[0045]

Embedded image

In the formula [II], A represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms. R ¹ has ¹ carbon
Represents an alkyl group having from 6 to 6, a halogen atom or an alkoxy group having from 1 to 6 carbon atoms. m represents an integer of 0 to 5. (17) General formula [III]

[0047]

Embedded image

In the formula [III], A represents a hydrogen atom, a halogen atom or an alkyl group, and X represents an oxygen atom or N.
H or N—R ₅ (wherein R ₅ represents an alkyl group), R ₁ , R ₂ , R ₃ , and R ₄ are each independently a hydrogen atom, a halogen atom, an alkyl group, or a substituted group. alkyl group, an aryl group, a substituted aryl group, -OR _6, -OC
_{O-R 7, -NHCO-R} 8, -NHCONHR 9, -
OCONH-R ₁₀ , -COOR ₁₁ , -CONHR ₁₂ ,-
COR ₁₃ , -CONR ₁₄ R ₁₅ , -CN, or -CH
Represents an O group, or R ₁ , R ₂ , R ₃ , and R ₄ are
Two of them may combine to form a ring, and R ₆ ~
R ₁₅ represents an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group. However, at least one of R ₁ , R ₂ , R ₃ , and R ₄ represents a group other than a hydrogen atom. (18) General formula [IV]

[0049]

Embedded image

In the formula [IV], A represents a hydrogen atom, a halogen atom or an alkyl group, X represents an oxygen atom, NH,
Or N—R ₅ (wherein R ₅ represents an alkyl group), and R ₁ , R ₂ , R ₃ , and R ₄ are each independently a hydrogen atom, a halogen atom, an alkyl group, or a substituted alkyl group. , an aryl group, a substituted aryl group, -OR _6, -OC
_{O-R 7, -NHCO-R} 8, -NHCONHR 9, -
OCONH-R ₁₀ , -COOR ₁₁ , -CONHR ₁₂ ,-
COR ₁₃ , -CONR ₁₄ R ₁₅ , -CN, or -CH
Represents an O group, or R ₁ , R ₂ , R ₃ , and R
₄ may form a ring with two of the carbon atoms to which it is attached, R _{6 to} R ₁₅ are alkyl groups,
It represents a substituted alkyl group, an aryl group, or a substituted aryl group, and L represents a divalent organic group. (19) In formula (V) - (CH ₂ -CA _{[(B) m - (X)} n -NH-Y ]) - (V) (wherein [V], A is a hydrogen atom, a halogen atom or a carbon .B a phenylene group represented by C1-4 alkyl groups, .X to represent a substituted phenylene group -CO-, or -SO ₂ - and .Y are -CO-R ₁ or -SO ₂ -R ₁ representing the Represents R ₁
Represents an alkyl group, a substituted alkyl group, an aromatic group or a substituted aromatic group. m and n represent 0 or 1, but m and n are not 0 at the same time. ). (20) General formula [VI]

[0051]

Embedded image

(21) General formula [VII]

[0053]

[Chemical 6]

(22) General formula [VIII]

[0055]

[Chemical 7]

(23) General formula [IX]

[0057]

Embedded image

(24) General formula [X]

[0059]

Embedded image

[In the formulas [VI] to [X], 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 represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, 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 or a naphthylene group which may have a substituent. ] (25) General formula [XI]

[0061]

Embedded image

(26) General formula [XII]

[0063]

Embedded image

In the formulas [XII] (a) to (d), X ¹ , X ² , X
³ each -O- or -NR ¹² - shows the. R ¹ , R
⁴ , R ⁷ and R ⁹ each represent —H or —CH ₃ .
R ^2, R ^5, alkylene group R ¹⁰ C ₁ which may have a substituent -C _12, cycloalkylene group, an arylene group, an aralkylene group. R ³ represents —H, an optionally substituted C ₁ -C ₁₂ alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. Also R
⁶ , R ⁸ and R ¹¹ are C _{1 to} C which may have a substituent.
_{And 12} alkyl groups, cycloalkyl groups, aryl groups and aralkyl groups. R ¹² represents a hydrogen atom or a C ₁ -C ₁₂ alkyl group which may have a substituent, a cycloalkyl group, an aryl group or an aralkyl group. General formula [XII]
(A), [XII] (b), [XII] (c) or [XII
Among the low molecular weight compounds represented by (d), those particularly preferably used in the present invention are those in which R ² , R ⁵ and R ¹⁰ are each a C _{2 to} C ₆ alkylene group, a cycloalkylene group or a substituent. A phenylene group which may have a group, a naphthylene group, R ³ is H or a C ₁ -C ₆ alkyl group, a cycloalkyl group or a phenyl group which may have a substituent, a naphthyl group, , R ⁶ , R ⁸ and R ¹¹ are C _{1 to} C ₆ alkyl groups, cycloalkyl groups or optionally substituted phenyl groups and naphthyl groups,
R ₁₂ represents hydrogen.

Such alkali-soluble film-forming resins can be used alone or in combination of two or more, and are used in an amount of 1 to 50% by weight of the total photosensitive composition. More preferably, it is 5 to 30% by weight. In addition to the above-mentioned copolymer, active methylene group-containing resin, polyvinyl butyral resin, polyurethane resin, polyamide resin, epoxy resin and the like can be used. Among them, particularly, the copolymers having the structural units of acrylonitrile, methacrylonitrile and (6) in (16) and (14) or the copolymers having the structural units of (2) and (6). Is preferred.

The other main component of the photosensitive composition of the present invention, the o-naphthoquinonediazide compound, comprises an o-quinonediazide sulfonic acid ester of a polyhydroxy compound. Examples of the polyhydroxy compound include low molecular weight compounds such as 2,3,4-trihydroxybenzophenone, pyrogallol and gallic acid, or polycondensation resins with 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 and thymol, divalent phenols such as catechol, resorcinol and hydroquinone, and pyrogallol. , Trihydric phenols such as phloroglucin, and the like. As the aldehyde, formaldehyde, benzaldehyde, acetaldehyde,
Examples include crotonaldehyde and furfural. Specific examples of the polycondensation resin include phenol / formaldehyde resin, m-cresol / formaldehyde resin, m- and p-mixed cresol / formaldehyde resin, resorcin / benzaldehyde resin, and pyrogallol / acetone resin.

Further, as the o-quinonediazide compound used in the present invention, the following compounds described in JP-A-58-43451 can also be used. That is, for example, 1, 2
-Benzoquinonediazidesulfonic acid ester, 1,2-
Known 1,2-naphthoquinone diazide sulfonic acid ester, 1,2-bennoquinone diazide sulfonic acid amide, 1,2-naphthoquinone diazide sulfonic acid amide, etc.
-Quinonediazide compounds, more specifically J. Kosar, "Light-Sensitive Systems," pages 339-352 (1965), John Willie & Sons (John). "Photoresist", Volume 50 (1975) by Willey & Sons, Inc. (New York) and W. S. De Forest.
1,2-Benzoquinonediazide-4-sulfonic acid phenyl ester, 1,2,1 ', 2'-di-, described in McGraw Hill Company (New York).
(Benzoquinonediazide-4-sulfonyl) -dihydroxybiphenyl, 1,2-benzoquinonediazide-4-
(N-ethyl-M-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-naphthoquinonediazide-5-sulfonyl) -aniline, 2 '-(1,2-naphthoquinonediazide-5-sulfonyloxy) -1-hydroxy-anthraquinone, 1,2- Naphthoquinonediazide-5-sulfone-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 4,4'-dihydroxy-1,
Condensate with 1 mol of 1'-diphenyl sulfone, 1,2-
Condensation product of 2 mol of naphthoquinonediazide-5-sulfonic acid chloride and 1 mol of 4,4'-diaminobenzophenone, condensation product of 1 mol of 1,2-naphthoquinonediazide-5-sulfonic acid chloride and 1 mol of purpurogallin, 1,
An example is a 1,2-quinonediazide compound such as 2-naphthoquinonediazide-5- (N-dihydroapiethyl) -sulfonamide. In addition, Japanese Patent Publication No. 37-19
No. 53, No. 37-3627, No. 37-13109,
No. 40-26126, No. 40-3801, No. 45-
No. 5604, No. 45-27345, No. 51-1301
The 1,2-quinonediazide compounds described in No. 3 and each publication can also be mentioned.

Of the above o-quinonediazide compounds,
A compound obtained by reacting 1,2-benzoquinone diazide sulfonyl chloride or 1,2-naphthoquinone diazide sulfonyl chloride with a condensation resin is preferable. Further, these are preferably 4-position substitution and 5-position substitution. Specific examples of the o-quinonediazide compound are described in JP-A-47-530.
3, the same 48-63802, the same 48-63803, the same 48
-96575, ibid 48-13354, ibid 49-3870.
1, the same 56-1044, the same 56-1045, Japanese Patent Publication 41
-11222, 45-9610, 49-1748.
1, 43-28403, JP-A-51-139402,
58-150948, 58-203434, 59-165053, 60-12145, 6
0-1342358, 60-163043, 6
1-118744, 62-10645, 62-
No. 10646, No. 62-153950, No. 62-17
8562, 64-76047, U.S. Pat. No. 3,1.
02,809, 3,126,281, 3,
No. 130,047, No. 3,148,983, No. 3,184,310, No. 3,188,210, No. 4,639,406, No. 2,797,213,
No. 3,046,120, No. 3,188,210
No. 3,454,400, No. 3,544,32
No. 3, No. 3,573,917, No. 3,674,4
95, 3,785,825, British Patents 1,22
No. 7,602, No. 1,251,345, No. 1,2
67,005 etc. and each thing described in each publication or specification can be mentioned.

Of these, preferred are o-quinonediazide sulfonic acid esters of polyhydroxy compounds having a weight average molecular weight of 2,000 or more. Examples of the polyhydroxy compound include pyrogallol / acetone resin, resorcin benzaldehyde, 2-methylresorcin / acetone resin, phenol-formaldehyde resin, cresol formaldehyde resin, hydroxystyrene resin and halogenated hydroxystyrene resin.
Sometimes pyrogallol-acetone resin is preferred. When synthesizing an o-naphthoquinonediazide compound from these polyhydroxy compounds, it is preferable to react 1,2-diazonaphthoquinonesulfonic acid chloride with 0.2 to 1.2 equivalents relative to the hydroxyl group of the polyhydroxy compound, It is more preferable to react 0.3 to 1.0 equivalent. As the 1,2-diazonaphthoquinonesulfonic acid chloride, 1,2-diazonaphthoquinone-5-sulfonic acid chloride or 1,2-diazonaphthoquinone-4-sulfonic acid chloride can be used.

The obtained o-naphthoquinonediazide compound is a mixture of 1,2-diazonaphthoquinonesulfonic acid ester groups having different positions and introduction amounts, but all of the hydroxyl groups are 1,2-diazonaphthoquinonesulfone. The ratio of the acid esterified compound in the mixture (content of the completely esterified compound) is preferably 5 mol% or more, more preferably 20 to 99 mol%. The amount of these o-quinonediazide compounds in the total amount of the photosensitive composition of the present invention is suitably 10 to 50% by weight, more preferably 15% by weight.
４０40% by weight. These may be used alone,
You may use it in combination of 2 or more type. Further, as the positive-working photosensitive substance other than the o-naphthoquinonediazide compound, for example, a polymer compound having an orthonitrocarbinol ester group described in JP-B-56-2696 may also be used in the present invention. You can

Further, a compound which generates an acid by photolysis,
A mixture with a compound having a C—O—C group or a C—O—Si group which dissociates with an acid can also be used in the present invention as a photosensitive substance. For example, a combination of a compound capable of generating an acid by photolysis with an acetal or O, N-acetal compound (JP-A-48-89003) or an orthoester or amide acetal compound (JP-A-51-
120714) and a polymer having an acetal or ketal group in the main chain (JP-A-53-133429).
No.) and an enol ether compound (JP-A-55)
No. 12995), a combination with an N-acyliminocarbonate compound (JP-A-55-126236), and a polymer having an orthoester group in the main chain (JP-A-56-1).
7345), a combination with a silyl ester compound (JP-A-60-10247), and a combination with a silyl ether compound (JP-A-60-37549, JP-A-60-121).
No. 446) and the like. These positive-working photosensitive substances are preferably 5 to 80% by weight, more preferably 10 to 50% by weight, based on the total weight of the composition.
In the photosensitive composition.

[0072]

[Oil-sensitizing agent] Further, as described in US Pat. No. 4,123,279, a substituent having an alkyl group having 3 to 8 carbon atoms such as t-butylphenolformaldehyde resin and octylphenolformaldehyde resin is substituted. It is preferable to use a condensate of phenol and formaldehyde or an o-quinonediazide sulfonic acid ester thereof in combination in order to improve the oil sensitivity of the image.
Further, the compounds described in JP-B-3-40380 and 3-40381 are also effective. Furthermore, the following general formula [XII1]
Compounds represented by are also preferable. That is, it is a condensation resin of substituted phenols and aldehydes and / or an o-naphthoquinonediazide sulfonic acid ester compound of the resin.

[0073]

[Chemical 12]

In the substituted phenols represented by the above general formula [XII1], R ⁵ and R ⁶ each include a hydrogen atom and an alkyl group (having 1 to 3 carbon atoms. 1 to 2 carbon atoms) Is particularly useful.) Or a halogen atom (a chlorine atom and a bromine atom are preferable for the internal atoms of each of fluorine, chlorine, bromine and iodine), and R ⁷ is an alkyl group having 2 or more carbon atoms. A group (preferably having 15 or less carbon atoms and 3 carbon atoms)
Alkyl groups from 8 to 8 are particularly useful. ) Or a cycloalkyl group (including those having 3 to 15 carbon atoms. A cycloalkyl group having 3 to 8 carbon atoms is particularly useful).

Examples of the above substituted phenols include isopropylphenol, tert-butylphenol, t
ert-amylphenol, hexylphenol, te
Examples thereof include rt-octylphenol, cyclohexylphenol, 3-methyl-4-chloro-5-tert-butylphenol, isopropylcresol, tert-butylcresol, tert-amylcresol, hexylcresol, tert-octylcresol, cyclohexylcresol and the like. Particularly preferred are tert-octylphenol and tert-butylphenol.

Examples of the above aldehydes include formaldehyde, benzaldehyde, acetaldehyde,
Examples thereof include aliphatic and aromatic aldehydes such as acrolein, crotonaldehyde and furfural, and include those having 1 to 6 carbon atoms. Of these, formaldehyde and benzaldehyde are preferred. The resin obtained by condensing the substituted phenols and the aldehydes is synthesized by polycondensing the substituted phenol represented by the general formula [XII1] and the aldehydes in the presence of an acidic catalyst. Further, o-quinonediazide sulfonic acid may be esterified. Further, a novolak resin having at least one carboxyl group, a hydroxyl group and an alkyl group of C ₄ or more described in JP-A-7-128844 or an o-quinonediazide sulfonic acid ester thereof is also preferable. Specifically, examples of the resin include hydroxybenzoic acid-xylenol-formaldehyde resin, butylbenzoic acid-xylenol-formaldehyde resin,
Lauric acid salicylic acid-xylenol-formaldehyde resin, stearic salicylic acid-xylenol-formaldehyde resin, hydroxybenzoic acid-butylphenol-formaldehyde resin, butylbenzoic acid-butylphenol-formaldehyde resin, laurylsalicylic acid-butylphenol-formaldehyde resin, stearic salicylic acid-butylphenol-formaldehyde resin. , Propylsalicylic acid-phenol-formaldehyde resin, dioxybenzoic acid-butyraldehyde resin, and the like, and of these, preferably hydroxybenzoic acid-butylphenol-formaldehyde resin, laurylsalicylic acid-butylphenol-formaldehyde resin, butylbenzoic acid-butylphenol-formaldehyde. It is a resin or the like. The addition amount is preferably 0.05 to 15% by weight.

[0077]

[Development Accelerator] The photosensitive composition of the present invention contains a cyclic acid anhydride for the purpose of increasing sensitivity and developing property.
Phenols and organic acids are preferably added. As the cyclic acid anhydride, US Pat. No. 4,115,128 is used.
, Phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-endooxy-Δ ⁴ -tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride , Α-phenyl maleic anhydride, succinic anhydride,
Pyromellitic anhydride and the like can be used. As phenols, bisphenol A, p-nitrophenol, p
-Ethoxyphenol, 2,4,4'-trihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 4-hydroxybenzophenone, 4,4 ',
4 "-trihydroxy-triphenylmethane, 4,
4 ', 3 ", 4"-tetrahydroxy-3,5,3',
5'-tetramethyltriphenylmethane and the like.

Further, as organic acids, JP-A-60-8 is used.
No. 8942, JP-A-2-96755 and the like, there are sulfonic acids, sulfinic acids, alkyl sulfates, phosphonic acids, phosphoric esters and carboxylic acids, and specifically, p-toluene sulfone Acid, dodecylbenzenesulfonic acid, p-toluenesulfinic acid, ethyl sulfate, phenylphosphonic acid, phenylphosphinic acid, phenyl phosphate, diphenyl phosphate, benzoic acid, isophthalic acid, adipic acid, p-toluic acid,
3,4-dimethoxybenzoic acid, phthalic acid, terephthalic acid, 1,4-cyclohexene-2,2-dicarboxylic acid,
Erucic acid, lauric acid, n-undecanoic acid, ascorbic acid and the like can be mentioned. Furthermore, the following acids are also effective,
Azelaic acid, q-toluic acid, β-ethylglutaric acid, m-oxybenzoic acid, p-oxybenzoic acid, 3,5
-Dimethyl benzoic acid, glyceric acid, glutaconic acid, glutaric acid, p-anisic acid, succinic acid, sebacic acid, β,
β-diethylglutaric acid, 1,1-cyclobutanedicarboxylic acid, 1,3-cyclobutanedicarboxylic acid, 1,1-
Cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid,
β, β-Dimethylglutaric acid, dimethylmalonic acid, α-
Tartaric acid, speric acid, pimelic acid, fumaric acid, β-propylglutaric acid, propylmalonic acid, mandelic acid, mesotartaric acid, β-methylglutaric acid, β, β-methylpropylglutaric acid, methylmalonic acid, malic acid, 1 , 1-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid,
1,4-cyclohexanedicarboxylic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, undecenoic acid, n
-Capric acid, pelargonic acid, mesitylenesulfonic acid,
Sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, m-benzenedisulfonic acid, etc., benzylsulfinic acid, sulfinic acids such as methanesulfinic acid, phosphonic acids such as methylphosphonic acid, chloromethylphosphonic acid, formic acid, acetic acid, propion Acids, butyric acid, isobutyric acid, pentanoic acid, hexanoic acid, heptanoic acid and other aliphatic monocarboxylic acids, cyclohexanecarboxylic acid and other alicyclic monocarboxylic acids, o-, m-, p-hydroxybenzoic acid,
o-, m-, p-methylbenzoic acid, 3,5-dihydroxybenzoic acid, phloroglysin carboxylic acid, gallic acid,
Aromatic monocarboxylic acids such as 3,5-dimethylbenzoic acid may be mentioned. Further, saturated or unsaturated aliphatic dicarboxylic acids such as malonic acid, dimethylmalonic acid, glital acid, adipic acid, suberic acid, azelaic acid and itaconic acid, alicyclic dicarboxylic acids such as tetrahydrophthalic acid, aromatic dicarboxylic acids and the like. Can be mentioned. The proportion of the above-mentioned cyclic acid anhydrides, phenols and organic acids in the photosensitive composition is preferably from 0.05 to 15% by weight, more preferably from 0.1 to 5% by weight.

[0079]

[Development Stabilizer] Further, in the photosensitive composition of the present invention, in order to broaden the stability of processing (so-called development latitude) with respect to developing conditions, JP-A-62-251740 and JP-A-4-68355 are used. Alternatively, JP-A-7-
Nonionic surfactants as described in JP-A-92689, JP-A-59-121044, JP-A-4-
Amphoteric surfactants such as those described in 13149 can be added.

Specific examples of the nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan trioleate, stearic acid monoglyceride, polyoxyethylene sorbitan monooleate, polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl. Ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene higher alcohol ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan monolaurate, poly Oxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan tristearate,
Polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbit tetraoleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol monooleate,
Examples thereof include polyethylene glycol distearate, polyoxyethylene nonylphenyl ether formaldehyde condensate, oxyethyleneoxypropylene block copolymer, polyethylene glycol and tetraethylene glycol.

Specific examples of the amphoteric surfactant include alkyldi (aminoethyl) glycine, alkylpolyaminoethylglycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine and N-tetradecyl-N. , N-betaine type (for example, trade name Amogen K, manufactured by Daiichi Kogyo Co., Ltd.) and alkyl imidazoline type (for example, trade name Levon 15, manufactured by Sanyo Kasei Co., Ltd.). The proportion of the nonionic surfactant and the amphoteric surfactant in the photosensitive composition is preferably 0.05 to 15% by weight, more preferably 0.1 to 5% by weight.

[0082]

[Print-Out Agent and Dye] In the photosensitive composition of the present invention, a print-out agent for obtaining a visible image immediately after exposure and a dye or pigment as an image colorant can be added. Typical examples of the printout agent include a combination of a compound that releases an acid upon exposure (photoacid releasing agent) and an organic dye capable of forming a salt. More specifically,
Combinations of o-naphthoquinonediazide-4-sulfonic acid halogenide and salt-forming organic dyes described in JP-A-36209 and JP-A-53-8128,
No. 36223, No. 54-74728, No. 60-362
No. 6, No. 61-143748, No. 61-151644
No. 63-58440, No. 60-241049,
No. 55-77742, No. 60-3626, No. 60-
177340, 61-143748 and 48
The combination of the trihalomethyl compound and the salt-forming organic dye described in each publication of No. 36281 can be mentioned. Such trihalomethyl compounds include oxazole-based compounds and triazine-based compounds, both of which have excellent stability over time and give a clear printout image.

On the other hand, the diazonium salt compound is preferably a diazonium salt which generates a strong Lewis acid upon exposure, and the counterion of an inorganic compound is recommended as the counterion portion. As a specific example of such a compound, the anion portion of the diazonium salt is at least one kind of phosphorus fluoride ion, arsenic fluoride ion, antimony fluoride ion, antimony chloride ion, tin chloride ion, bismuth chloride ion and zinc chloride ion. An aromatic diazonium salt may be mentioned, and preferably a paradiazophenylamine salt may be mentioned. The amount of the compound that forms a halogen free radical upon irradiation with the above-mentioned actinic ray in the entire photosensitive layer is 0.
3 to 15% by weight is preferable. The light-sensitive lithographic printing plate preferably contains a compound that forms a halogen free radical upon irradiation with the above-mentioned actinic ray, and a color-changing agent that changes the color tone by interacting with the photolysis product. There are two types of such discoloring agents, one that develops color and the other that discolors or discolors. As the discoloring agent that discolors or discolors, various dyes such as diphenylmethane type, triphenylmethane type, thiadia type, oxazine type, phenazine type, xanthene type, anthraquinone type, iminonaphthoquinone type and azomethine type are effectively used.

Specific examples of these are as follows. Brilliant Green, Eosin,
Ethyl Violet, Erythrosin B, Methyl Green, Crystal Violet, Basic Fuchsine, Phenolphthalein, 1,3-Diphenyltriazine,
Alizarin Red S, thymolphthalein, methyl violet 2B, quinaldine red, rose bengal, methanyl yellow, thymol sulfophthalein, xylenol blue, methyl orange, orange IV, diphenylthiocarbazone, 2,7-dichlorofluorescein, para Methyl Red, Congo Red, Benzopurpurin 4
B, α-naphthyl red, Nile blue 2B, Nile blue A, phenacetaline, methyl violet, malachite green, parafuchsin, Victoria pure blue BOH (Hodogaya Chemical Co., Ltd.), oil blue # 60
3 [manufactured by Orient Chemical Industry Co., Ltd.], Oil Pink # 3
12 [manufactured by Orient Chemical Industry Co., Ltd.], Oil Red 5
B [manufactured by Orient Chemical Industry Co., Ltd.], oil scarlet # 308 [manufactured by Orient Chemical Industry Co., Ltd.], oil red OG [manufactured by Orient Chemical Industry Co., Ltd.], oil red RR [manufactured by Orient Chemical Industry Co., Ltd.] , Oil Green # 502 [manufactured by Orient Chemical Industry Co., Ltd.], Spiron Red BEH Special [Hodogaya Chemical Industry Co., Ltd.]
], M-cresol purple, gresol red, rhodamine B, rhodamine 6G, first acid violet R, sulforhodamine B, auramine, 4-p
-Diethylaminophenyliminonaphthoquinone, 2-carboxyanilino-4-p-diethylaminophenyliminonaphthoquinone, 2-carbostearylamino-4-
p-dihydroxyethylamino-phenyliminonaphthoquinone, p-methoxybenzoyl-p'-diethylamino-o'-methylphenyliminoacetanilide, cyano-p-diethylaminophenyliminoacetanilide, 1-phenyl-3-methyl-4-p-diethylamino Phenylimino-5-pyrazolone, 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

Further, arylamines can be used as the color-changing agent that develops color. Aryl amines suitable for this purpose include so-called leuco dyes in addition to simple aryl amines such as primary and secondary aromatic amines, and examples thereof include the following. Diphenylamine, dibenzylaniline, triphenylamine, diethylaniline, diphenyl-p-phenylenediamine, p-toluidine, 4,4'-biphenyldiamine, o-chloroaniline, o-bromoaniline, 4-chloro-o-phenylenediamine. , O-bromo-N, N-dimethylaniline, 1,2,3-triphenylguanidine, naphthylamine, diaminodiphenylmethane, aniline, 2,5-dichloroaniline, N-methyldiphenylamine, o-toluidine, p, p'- Tetramethyldiaminodiphenylmethane, N, N-dimethyl-p-phenylenediamine, 1,2-dianilinoethylene, p, p ', p "-hexamethyltriaminotriphenylmethane, p, p'-tetramethyldiaminetriphenyl Methane, p, p'- Tiger methylamino diaminodiphenyl methyl imine, p, p ', p "- triamino -
o-methyltriphenylmethane, p, p ′, p ″ -triamino-triphenylcarbinol, p, p′-tetramethyldiphenyl-4-anilinonaphthylmethane, p,
p ′, p ″ -triamino-triphenylmethane, p,
p ', p "-hexapropyltriaminotriphenylmethane can be mentioned.
The dye described in JP-B-47 is particularly preferred. The proportion of the discoloring agent in the photosensitive layer is preferably 0.01 to 10% by weight.

[0086]

[Plasticizer] In addition to the above materials, the photosensitive composition may further contain a plasticizer, a surfactant and the like, if necessary. For example, as a specific plasticizer, phthalic acid ester, phosphoric acid ester, fatty acid ester, glycol derivative triacetylene, chlorinated paraffin, castor oil and the like are preferable, and specifically, for example, di-2-ethylhexyl adipate, adipic acid. (N-hexyl-n-octyl-n
-Decyl), di-2-ethylhexyl azelate, dibutyl sebacate, di-2-ethylhexyl sebacate, di-2-ethylhexyl dodecanedioate, dimethyl phthalate, dibutyl phthalate, diheptyl phthalate, phthalate-2- Examples thereof include ethylhexyl, di-2-ethylhexyl phthalate, diisodecyl phthalate, tributyl trimellitate, tri-2-ethylhexyl trimellitate, triethyl phosphate and tricresyl phosphate.

[0087]

[Coating Solvent] The photosensitive composition of the present invention is dissolved in a solvent capable of dissolving the above-mentioned components and coated on the aluminum plate of the support. As the solvent used here, an organic solvent described in JP-A-61-95463 is used alone or in combination. For example, 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, methyl dipropylene glycol dicarboxylate. Ether, dipropylene glycol methyl ethyl ether, ethyl formate, propyl formate, butyl formate, amyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate,
Ethyl butyrate, dimethylformamide, dimethyl sulfoxide, dioxane, acetone, methyl ethyl ketone, cyclohexanone, methylcyclohexanone, diacetone alcohol, acetylacetone, γ-butyrolactone,
Propylene glycol monomethyl ether and its acetate, propylene glycol monoethyl ether and its acetate, dipropylene glycol monomethyl ether and its acetate, dipropylene glycol monoethyl ether and its acetate, tripropylene glycol monomethyl ether and its acetate, tripropylene glycol monoethyl Examples thereof include ethers and acetates thereof, tetrahydrofuran, methylene chloride, methylpropyl ketone, methylbutyl ketone, diethyl ketone, cyclohexanol and n-butyl alcohol, benzyl alcohol, phenethyl alcohol and the like.

The photosensitive composition of the present invention contains 2 to 50% by weight.
Is dissolved and dispersed at a solid content concentration of, and coated and dried on a support.

[0089]

[Coating amount] The coating amount of the layer of the photosensitive composition (photosensitive layer) coated on the support varies depending on the use, but is generally 0.3 to 4.0 g / dry weight. m ² is preferred. As the amount of coating decreases, the amount of exposure for obtaining an image may be small, but the film strength is reduced. As the coating amount increases, the exposure amount is required, but the photosensitive film becomes stronger. For example, when used as a printing plate, a printing plate having a high printable number (high printing durability) can be obtained.

[0090]

[Improvement of coating surface quality] In the photosensitive composition of the present invention, a surfactant for improving coating surface quality, for example, a fluorine-based interface as described in JP-A-62-170950 is used. Activators can be added. A preferable addition amount is 0.001 to 1.0% by weight of the whole photosensitive composition.
And more preferably 0.005 to 0.5% by weight.

[0091]

[Matt layer] A mat layer is provided on the surface of the photosensitive layer provided as described above in order to reduce the vacuuming time during contact exposure using a vacuum baking frame and to prevent baking blur. Is preferred. Specifically, JP-A-50-1258
No. 05, Japanese Patent Publication No. 57-6582, No. 61-28986
And a method in which a solid powder is thermally fused as described in JP-B-62-62337.

Examples of the photosensitive layer of the negative photosensitive lithographic printing plate according to the invention include a photosensitive layer made of a photocrosslinkable polymer and a photosensitive layer made of a photosensitive diazo resin. Examples of the photosensitive diazonium compound used in the photosensitive layer composed of the photosensitive diazo resin include those shown in the following (I), (II) and (III). (I) An aromatic compound having at least one of a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a sulfinic acid group, and an oxygen acid group of phosphorus, and the following general formula [XIV]
Co-condensed diazo resin containing an aromatic diazonium compound represented by

[0093]

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In the formula [XIV], R ¹ represents a hydrogen atom, an alkyl group which may have a substituent, a hydroxyl group, a carboxyester group or a carboxyl group, preferably a hydrogen atom and a carbon number of 1 to 5 Is an alkyl group or a hydroxyl group. R ² represents a hydrogen atom, an alkyl group or an alkoxy group, preferably a hydrogen atom or a methoxy group. R ³ represents a hydrogen atom, an alkyl group or an alkoxy group, preferably a hydrogen atom. X ⁻ represents an anion, preferably an aliphatic or aromatic sulfonate anion, and Y represents —NH—, —O— or —S—. The aromatic ring of the aromatic compound is preferably a phenyl group or a naphthyl group. The above-mentioned carboxyl group, phenolic hydroxyl group, sulfonic acid group, sulfinic acid group, and oxygen acid group of phosphorus may be directly bonded to the aromatic ring or may be bonded via a linking group. Examples of the linking group include groups having 1 or more carbon atoms containing an ether bond. (II) Diazo resin having at least one repeating unit represented by the following general formula [XV]

[0095]

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In the formula [XV], R ⁴ is a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a sulfinic acid group or an oxygen acid group of phosphorus, or a group having at least one of these and having 15 or less carbon atoms. R ¹ , R ² , R ³ , X ⁻ and Y are the same as the groups represented by the above general formula [XIV]. (III) at least one of a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a sulfinic acid group and an oxygen acid group of phosphorus is replaced by a compound represented by the general formula [XVI], [XVII] or [XV
III] A diazo resin obtained by a condensation reaction of an aromatic diazonium compound having a form as shown in [III] with an aldehyde or ketone or an equivalent of an active carbonyl compound thereof.

[0097]

[Chemical 15]

In the formulas [XVI] to [XVIII], R^FourIs carbo
Xyl group, phenolic hydroxyl group, sulfonic acid group, sulf
A phosphoric acid group or an oxygen acid group of phosphorus, R¹, R²,
R^Three, X ^-And Y are groups represented by the above general formula [XIV].
Is the same as. Further, n is 0, 1 or 2. Book
Counter anion X of diazo resin used in the invention^-As special
Preferred are butyl naphthalene sulfonic acid, dibutyl
Lunaphthalenesulfonic acid, hexafluorophosphoric acid, 2-
Hydroxy-4-methoxybenzophenone-5-sulfo
Acid, dodecylbenzene sulfonic acid. Used in the present invention
The diazo resin used has a molar ratio of each monomer and a condensation line.
By changing the conditions variously, the molecular weight can be set to an arbitrary value.
Can be obtained with a molecular weight of about 400 to 100,0
00, preferably about 800 to 5,000
Is appropriate. The above photosensitive diazo resin is an alkali
Soluble or swellable lipophilic polymer compound as a binder
-Use as a resin and use in combination with this
desirable.

Examples of such lipophilic polymer compounds are:
Examples thereof include copolymers having the structural units of the monomers shown in the following (1) to (14) and having a molecular weight of usually 100,000 to 200,000. (1) Acrylamides, methacrylamides, acrylic acid esters, methacrylic acid esters and hydroxystyrenes having aromatic hydroxyl groups, such as N- (4-
(Hydroxyphenyl) acrylamide or N- (4-hydroxyphenyl) methacrylamide, o-, m-, p
-Hydroxyphenyl-acrylate or methacrylate, o-, m-, p-hydroxystyrene, (2) acrylic acid esters having an aliphatic hydroxyl group, and methacrylic acid esters such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate. ,
(3) Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride, and itaconic acid, (4) methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, acrylic (Substituted) alkyl acrylates such as octyl acid, 2-chloroethyl acrylate, glycidyl acrylate, N-dimethylaminoethyl acrylate, (5) methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, cyclohexyl methacrylate, 4- (Substituted) alkyl methacrylates such as hydroxybutyl methacrylate, glycidyl methacrylate, N-dimethylaminoethyl methacrylate, (6) acrylamide,
Methacrylamide, N-methylolacrylamide, N
-Acrylamide such as methylol methacrylamide, N-ethyl acrylamide, N-hexyl methacrylamide, N-cyclohexyl acrylamide, N-hydroxyethyl acrylamide, N-phenyl acrylamide, N-nitrophenyl acrylamide, N-ethyl-N-phenyl acrylamide or Methacrylamides (7) Ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, phenyl vinyl ether and other vinyl ethers, (8) vinyl acetate, vinyl chloroacetate, vinyl butyrate, Vinyl esters such as vinyl benzoate, (9) styrene, α-methylstyrene, chloromethylstyrene Styrenes, (10) methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, or phenyl vinyl ketone, (11)
Olefins such as ethylene, propylene, isobutylene, butadiene and isoprene, (12) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, acrylonitrile, methacrylonitrile, etc. (13) Maleimide, N-acryloylacrylamide, N -Unsaturated imides such as acetyl methacrylamide, N-propionyl methacrylamide, N- (p-chlorobenzoyl) methacrylamide, (14) N- (o-aminosulfonylphenyl) methacrylamide, N- (m-aminosulfonylphenyl) ) Methacrylamide, N- (p-amino) sulfonylphenylmethacrylamide, N- (1- (3-
Aminosulfonyl) naphthyl) methacrylamide, N-
Methacrylamides such as (2-aminosulfonylethyl) methacrylamide, and acrylamides having the same substituents as above, o-aminosulfonylphenyl methacrylate, m-aminosulfonylphenyl methacrylate, p-aminosulfonylphenyl methacrylate, Methacrylic acid esters such as 1- (3-aminosulfonylnaphthyl) methacrylate, and unsaturated sulfonamides such as acrylic acid esters having the same substituents as above.

Further, a monomer copolymerizable with the above-mentioned monomer may be copolymerized. Further, a copolymer obtained by copolymerizing the above-mentioned monomers may be modified with, for example, glycidyl methacrylate or glycidyl acrylate, but is not limited thereto. More specifically, a copolymer having a hydroxyl group or a sulfonamide group, containing the monomers listed in (1), (2) and (14) above, is preferable, and it has an aromatic hydroxyl group or a sulfonamide group. Copolymers are more preferred. The above copolymer preferably contains the unsaturated carboxylic acid listed in (3), and the preferable carboxylic acid value of the copolymer is 0 to 3
meq / g, more preferably 0.5 to 2.5 meq / g. The preferred molecular weight of the copolymer is from 150,000 to 150,000. If necessary, a polyvinyl butyral resin, a polyurethane resin, a polyamide resin, an epoxy resin, a novolak resin, a natural resin, or the like may be added to the copolymer. The lipophilic polymer compound used in the present invention is usually contained in the solid content of the photosensitive composition in an amount of 40 to 99% by weight, preferably 50 to 95% by weight. The photosensitive diazo resin used in the present invention is usually contained in an amount of 1 to 60% by weight, preferably 3 to 40% by weight.

A dye may be further used in the photosensitive composition of the present invention. The dye is used for the purpose of obtaining a visible image by exposure (exposed visible image) and a visible image after development. Preferably, triphenylmethane type and diphenylmethane type dyes are effectively used. Victoria Pure Blue BOH is particularly preferable. The above dye is usually contained in the photosensitive composition in an amount of 1 to 5% by weight.
Various additives can be added to the photosensitive composition of the present invention. In order to provide the above-mentioned photosensitive composition on a support, a photosensitive diazo co-condensation resin, a lipophilic polymer compound and, if necessary, various amounts of various additives are added in an appropriate solvent (methyl cellosolve, ethyl cellosolve). , Dimethoxyethane, diethylene glycol monomethyl ether, diethylene glycol-dimethyl ether, 1-methoxy-
2-propanol, methyl cellosolve acetate, acetone, methyl ethyl ketone, methanol, dimethylformamide, dimethylacetamide, cyclohexanone,
Dioxane, tetrahydrofuran, methyl lactate, ethyl lactate, ethylene dichloride, dimethyl sulfoxide,
Water or a mixture thereof) to prepare a coating solution of the photosensitive composition, apply the solution on a support, and dry the solution. The solid content concentration of the photosensitive composition at the time of application is 1 to 50.
It is desirable to be in the range of weight%. In this case, the coating amount of the photosensitive composition may be about 0.2 to 10 g / m ² (dry weight).

Examples of the photocrosslinkable polymer used in the photosensitive layer made of a photocrosslinkable polymer include polymers having a maleimide group, a cinnamyl group, a cinnamoyl group, a cinnamylidene group, a cinnamylidene acetyl group or a chalcone group in a side chain or a main chain. Is mentioned. As a polymer having a maleimide group in its side chain, JP-A-52-988 (corresponding US Pat.
079,041), German Patent No. 2,626,769, European Patent No. 21,019, European Patent No. 3,552, and Die Angewandte Makro Mulelare Chemie.
romolekulare Chemie) 115 (1983) 162-1.
The following general formula [XIX] described on page 82:

[0103]

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(In the formula [XIX], R ⁵ and R ⁶ each independently represent an alkyl group having a maximum of 4 carbon atoms, or R ⁵ and R ⁶ are taken together to form a 5-membered or 6-membered group. Member having a maleimide group represented by the formula (1) may be formed on the side chain thereof), and JP-A-49-128991.
Issue No. 49-128992, Issue No. 49-128993
No. 50, No. 50-5376, No. 50-5377, No. 50
-5379, 50-50378, 50-5380.
No. 53-5298, No. 53-5299, No. 53
-5300, 50-50197, 51-479.
No. 40, No. 52-13907, No. 50-45079.
No. 52-121700, No. 50-10884,
No. 50-45087, German Patent No. 2,349,948.
No. 2,616,276, the following general formula [XX]:

[0105]

Embedded image

(In the formula [XX], R ⁷ represents an aromatic group,
R ⁸ represents a hydrogen atom, a halogen atom, an alkyl group or a cyano group) and a polymer having a maleimide group represented by a side chain. The average molecular weight of these polymers is 1000 or more, preferably 30,000 to 40,000. Further, these polymers have an average of 2 or more maleimide groups in the side chain per molecule.

In order to make these polymers having maleimide groups in their side chains soluble or swellable in alkaline water, acid groups may be included in the polymers. Specific examples of the acid group include a carboxylic acid, a sulfonic acid, a phosphoric acid, a phosphonic acid, an alkali metal salt or an ammonium salt thereof, and a residue having a pka of 6 to 12 which is difficult to dissolve in alkaline water. _{, -SO 2 NHCO -, - CONHCO} -, - S
O ₂ NHCOO-, and a 4-hydroxyphenyl group. For example, the monomer having an acid group and the monomer having a maleimide group may be mixed in an amount of 10/90 to 50/5.
The polymer of the present invention can be easily obtained by copolymerizing at a ratio of 0, preferably 20 to 40/60 (molar ratio). The acid value of the maleimide polymer having an acid group is preferably in the range of 30 to 300, more preferably 5
0 to 200. Preferred examples of the monomer having a copolymerizable acid group include vinyl monomers having a carboxyl group such as acrylic acid and methacrylic acid, maleic anhydride, and itaconic anhydride. Among the polymers with these acid numbers, Die Angewadte Macromolleclare Chemie (Die Angewa
ndte Makromolekulare Chemie) 128 (1984), pages 71-91, a copolymer of N- [2-methacryloyloxy) ethyl] -2,3-dimethylmaleimide and methacrylic acid or acrylic acid is useful. Is. Furthermore, by synthesizing the vinyl monomer of the third component at the time of synthesizing the copolymer, a multi-component copolymer suitable for the purpose can be easily synthesized. For example, by using an alkyl methacrylate or an alkyl acrylate having a glass transition point of a homopolymer of room temperature or lower as a vinyl monomer of the third component, flexibility can be given to the copolymer.

Among the other photocrosslinkable polymers of the present invention having a cinnamyl group, a cinnamoyl group, a cinnamylidene group, a cinnamylideneacetyl group, a chalcone group or the like in the side chain or the main chain, a photosensitive cinnamoylene group is added to the main chain. Examples thereof include photosensitive polyesters described in U.S. Pat. No. 3,030,208, U.S. Pat. The above polyesters are made by condensing a suitable polycarboxylic acid, or a lower alkyl ester of a suitable polycarboxylic acid, or chloride with a suitable polyhydric alcohol in the presence of an esterification catalyst. Examples of these polymers solubilized in alkaline water include the following. That is, a polyester prepolymer having a photodimerizable unsaturated double bond adjacent to an aromatic nucleus, a side chain carboxyl group and a hydroxyl group at a terminal, in a main chain as described in JP-A-60-191244. A chain extender having two or more functional groups capable of reacting with a hydroxyl group in the molecule, for example, diisocyanate compound, diphenyl terephthalate, diphenyl carbonate and terephthaloyl bis (N-caprolactam)
Pyridine as a chain extender to a photosensitive polymer obtained by reacting the same, or a polyester prepolymer or polyurethane polymer having a photodimerizable unsaturated double bond adjacent to an aromatic nucleus in the main chain and a hydroxyl group at the terminal. Examples thereof include a photosensitive polymer in which a carboxyl group is introduced into a side chain by reacting with meritic acid dianhydride or cyclopentanetetracarboxylic acid dianhydride.

Further, in the side chain, a functional group capable of photoduplication,
Examples thereof include alkali water-soluble or swellable photosensitive polymers having a side chain with a carboxyl group and having an acid value of 20 to 200. These photosensitive polymers are disclosed in JP-A-62-1
175729, JP-A-62-175730, JP-A-63-25443, JP-A-63-218944, and JP-A-63-218945. The photo-crosslinkable polymer used in the present invention preferably has a molecular weight of 1,000 or more, preferably 10,000 to 500,000, and particularly preferably 20,000 to 300,000. The amount of the photocrosslinkable polymer added to the entire composition of the photosensitive layer is 10 to 10.
99% by weight (hereinafter abbreviated as%), preferably 50 to
99%.

The photosensitive layer made of a photocrosslinkable polymer preferably contains a photosensitive diazo resin in order to improve the adhesion to the support. As such a photosensitive diazo resin, the diazo resins represented by the above (I), (II) and (III) can be used. When the diazo resin is contained in the photosensitive layer, the content thereof is 0.1 to 30% by weight, preferably 1 to 10% by weight. In addition to the diazo resin used in the present invention, Japanese Patent Publication No. 47-1167
No. 50-118302, Japanese Patent Publication No. 52-736.
The diazo resin as described in JP-A No. 4 and JP-A No. 59-222834 may be used together in an amount of 50% by weight or less based on the diazo resin of the present invention.

A sensitizer can be used in the photosensitive layer used in the present invention. As such a sensitizer, 300
A triplet sensitizer having a maximum absorption that allows practically sufficient light absorption in the range of nm or more is preferable. Examples of such sensitizers include benzophenone derivatives, benzanthrone derivatives, quinones, aromatic nitro compounds, naphthothiazoline derivatives, benzothiazoline derivatives, thioxanthones, naphthothiazole derivatives, ketocoumarin compounds,
Examples thereof include benzothiazole derivatives, naphthofuranone compounds, pyrylium salts and thiapyrylium salts.
Specifically, Michler's ketone, N, N'-diethylaminobenzophenone, benzanthrone, (3-methyl-
1,3-diaza-1,9-benz) anthrone picramide, 5-nitroacenaphthene, 2-chlorothiosanthone, 2-isopropylthioxanthone, dimethylthioxanthone, methylthioxanthone-1-ethylcarboxylate, 2-nitrofluorene, 2-dibenzoylmethylene-3-methylnaphthothiazoline, 3,3-carbonyl-bis (7-diethylaminocoumarin), 2,4
6-triphenylthiapyrylium perchlorate, 2-
(P-chlorobenzoyl) naphthothiazole and the like can be mentioned. The amount of these sensitizers added is suitably about 1 to about 20% by weight, more preferably 3 to 10% by weight, based on the photosensitive layer.

The photosensitive layer according to the present invention may further contain a binder, if necessary, and is usually appropriately selected from linear organic polymers. Specific examples of the binder include chlorinated polyethylene, chlorinated polypropylene, polyacrylic acid alkyl ester, acrylic acid alkyl ester, acrylonitrile, vinyl chloride, styrene, a copolymer containing at least one kind of a monomer such as butadiene as a constitutional unit. , Polyamide, methyl cellulose, polyvinyl formal,
Examples include polyvinyl butyral, methacrylic acid copolymer, acrylic acid copolymer, and itaconic acid copolymer. In some cases, a dye or pigment or a pH indicator as a printout agent may be added for the purpose of coloring the photosensitive layer. Further, the photosensitive layer of the present invention may contain a plasticizer or the like. As the plasticizer, dialkyl phthalate such as dibutyl phthalate and dihexyl phthalate, oligoethylene glycol alkyl ester, phosphate plasticizer and the like can be used. Further, it is preferable to blend a thermal polymerization inhibitor and an antioxidant in the photosensitive layer, for example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol,
t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,
2'-Methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole and the like are mentioned as useful ones.

For the above-mentioned photosensitive layer, a photosensitive composition comprising the above components is prepared, for example, by using 2-methoxyethanol, 2-methoxyethyl acetate, methyl cellosolve, propylene glycol monomethyl ether, 3-methoxypropanol, 3-methoxypropyl. Acetate, acetone,
Methyl ethyl ketone, ethylene dichloride, methyl lactate, ethyl lactate, methanol, dimethylformamide,
It is formed by dissolving a suitable solvent such as ethanol or methyl cellosolve acetate alone or in a mixed solvent in which these are appropriately combined and coating the solution on a support. The coating amount in the range of about 0.1 g / m ² ~ about 10 g / m ² in weight after drying are suitable, preferably from 0.5 to 5 g / m ^2.

In the present invention, an intermediate layer is optionally used for the purpose of enhancing the adhesion between the support and the photosensitive layer, preventing the photosensitive layer from remaining in the developing solution, or preventing halation. May be provided. In order to improve the adhesion, the intermediate layer is generally made of a diazo resin, a phosphoric acid compound adsorbed on aluminum, or the like. The intermediate layer made of a substance having high solubility so that the photosensitive layer does not remain after development is generally made of a polymer having good solubility or a water-soluble polymer. Further, for antihalation purposes, the intermediate layer typically contains paints and UV absorbers. The thickness of the intermediate layer is arbitrary, and must be a thickness capable of performing a uniform bond-forming reaction with the upper photosensitive layer upon exposure. Usually, the coating ratio of about 1 to 100 mg / m ² on a dry solids well, 5 to 40 mg / m ² is particularly favorable. The proportion of the diazo resin used in the intermediate layer is 30 to 100% by weight, preferably 60 to 100% by weight.

[0115]

According to the treatment method of the present invention, the pH is relatively high.
It is possible to perform development with a safe developing solution having a low viscosity, and it is possible to achieve both developability and image strength (printing durability and chemical resistance).

[0116]

The present invention will be described in detail with reference to the following examples.

[0117]

[Preparation of support]

[Aluminum alloy] ◆ Aluminum alloy A (semi-continuous cast material) Si 0.082%, Fe 0.28%, Cu 0.016
%, Ti 0.014%, Mn 0.028%, B0.00
Cold-rolling a semi-continuous cast material containing 2% to a thickness of 3 mm,
An aluminum alloy sheet that was intermediate annealed at 500 ° C. for 4 hours, further cold-rolled to a thickness of 0.3 mm, and finally annealed at 250 ° C. for 4 hours. ◆ Aluminum alloy B (continuous casting material) Si 0.082%, Fe 0.28%, Cu 0.016
%, Ti 0.014%, Mn 0.028%, B0.00
Using a Hunter continuous casting and rolling mill containing 2%, plate thickness 7m
An aluminum alloy plate having a thickness of 0.30 mm by finally cold rolling, heat treating, straightening, etc. the aluminum alloy coil of m.

[Roughening Treatment] ◆ Roughening Treatment A The surface of the aluminum alloy is 0.480 mm in hair diameter and 10 hair in length.
A 0 mm nylon brush and an aqueous suspension of pumicetone having an average particle size of 15 to 35 μm were used, and after graining, they were thoroughly washed with water. 3% in 10% sodium hydroxide solution at 70 ℃
20% after immersing for 0 seconds and etching, and then rinsing with running water
It was neutralized and washed with HNO ₃ . Using a sinusoidal alternating waveform current under the condition of V _A (aluminum anode voltage) = 12.7 V, this was subjected to 160 coulomb in a 1% nitric acid aqueous solution.
The electrolytic surface-roughening treatment was performed so that the amount of electricity at the time of the aluminum anode was / dm ² . When the surface roughness was measured, it was 0.6.
It was μ (Ra indication). Subsequently, after soaking in a 1% sodium hydroxide aqueous solution at 40 ° C. for 30 seconds, 30% H ₂ S was added.
After being immersed in an O ₄ aqueous solution and desmutted at 55 ° C. for 2 minutes, a cathode is placed on the grained surface in a 20% H ₂ SO ₄ aqueous solution, and the weight of the anodic oxide film is 2 at a current density of 2 A / dm ² . A substrate was prepared by anodizing with direct current so as to obtain 0.5 g / m ² . ◆ Roughening treatment B The aluminum alloy surface has a hair diameter of 0.480 mm and a hair length of 10
A 0 mm nylon brush and an aqueous suspension of pumicetone having an average particle size of about 15 to 35 μm were used, and after graining, they were thoroughly washed with water. After immersing in a 10% sodium hydroxide aqueous solution at 70 ° C for 30 seconds for etching, and then rinsing with running water, 20
It was neutralized and washed with% HNO ₃ . Using a sinusoidal alternating waveform current under the condition of V _A (aluminum anode voltage) = 12.7 V, this was subjected to 160 coulomb in a 1% nitric acid aqueous solution.
The electrolytic surface-roughening treatment was performed so that the amount of electricity at the time of the aluminum anode was / dm ² . The surface roughness was measured and found to be 0.
It was 6 μ (Ra indication). Subsequently, after dipping in 1% sodium hydroxide aqueous solution at 40 ° C. for 30 seconds, 30% H ₂
After immersing in an SO ₄ aqueous solution and desmutting at 55 ° C. for 2 minutes, a cathode is placed on the grained surface in a 20% H ₂ SO ₄ aqueous solution and the anodized film weight is 1 at a current density of 2 A / dm ² . A substrate was prepared by anodizing with direct current so as to obtain 0.5 g / m ² . ◆ Roughening treatment C Aluminum alloy surface has a hair diameter of 0.480 mm and a hair length of 10
A 0 mm nylon brush and an aqueous suspension of pumicetone having an average particle size of about 15 to 35 μm were used, and after graining, they were thoroughly washed with water. After immersing in a 10% sodium hydroxide aqueous solution at 70 ° C for 30 seconds for etching, and then rinsing with running water, 20
It was neutralized and washed with% HNO ₃ . This is electrolyzed under the condition of V _A (anode voltage of aluminum) = 12.7V using a sinusoidal alternating current in a 1% aqueous nitric acid solution so as to obtain an electric quantity of 310 coulomb / dm ^{2 at} the time of aluminum anode. Roughening treatment was performed. The surface roughness was measured and found to be 0.
It was 6 μ (Ra indication). Subsequently, after dipping in 1% sodium hydroxide aqueous solution at 40 ° C. for 30 seconds, 30% H ₂
After soaking in an SO ₄ aqueous solution and desmutting at 55 ° C. for 2 minutes, a cathode is placed on the grained surface in a 20% H ₂ SO ₄ aqueous solution and the anodized film weight is 2 at a current density of 2 A / dm ² . A substrate was prepared by anodizing with direct current so as to obtain 0.5 g / m ² . ◆ Roughening treatment D The aluminum alloy surface has a hair diameter of 0.295 mm and a hair length of 80.
mm nylon brush and an aqueous suspension of pumicetone having an average particle diameter of about 15 to 35 μm were used, and after graining, they were thoroughly washed with water. 3% in 10% sodium hydroxide solution at 70 ℃
20% after immersing for 0 seconds and etching, and then rinsing with running water
It was neutralized and washed with HNO ₃ . This was subjected to 260 coulombs in a 1% nitric acid aqueous solution using a sinusoidal alternating current under the condition of V _A (anode voltage of aluminum) = 12.7V.
The electrolytic surface-roughening treatment was performed so that the amount of electricity at the time of the aluminum anode was / dm ² . When the surface roughness was measured, it was 0.4.
It was μ (Ra indication). Subsequently, after soaking in a 1% sodium hydroxide aqueous solution at 40 ° C. for 30 seconds, 30% H ₂ S was added.
After being immersed in an O ₄ aqueous solution and desmutted at 55 ° C. for 2 minutes, a cathode is placed on the grained surface in a 20% H ₂ SO ₄ aqueous solution, and the weight of the anodic oxide film is 2 at a current density of 2 A / dm ² . A substrate was prepared by anodizing with direct current so as to obtain 0.5 g / m ² . ◆ Roughening treatment E While supplying an aluminum plate with a suspension of pumice stone and water having an average particle diameter of about 15 to 35 μm on the aluminum surface,
Brush graining treatment was performed with a rotating nylon brush shown below. The first brush has a bristle length of 100 mm and a bristle diameter of 0.
720 mm, flocked density 70 / cm ² , second brush 80 mm in bristle length, 0.295 mm in bristles, 670 flocked density
It was / cm ² . The rotation of the brush roll is 250 rp
It was m. After the brush grains were thoroughly washed with water, they were immersed in a 10% aqueous sodium hydroxide solution at 60 ° C. for 20 seconds for etching, further washed with running water, neutralized with 20% nitric acid, and washed with water. These were electrolyzed in a 1% nitric acid aqueous solution under a condition of V _A (anode voltage of aluminum) = 12.7V to obtain an electric quantity of 160 coulomb / dm ^{2 in} an aqueous 1% nitric acid solution. Roughening treatment was performed. The surface roughness was measured and found to be 0.79μ (R
a). Then, after dipping in a 1% sodium hydroxide aqueous solution at 40 ° C. for 30 seconds, dipping in a 30% sulfuric acid aqueous solution and desmutting at 60 ° C. for 2 minutes, 20% H ₂
A cathode is placed on the grained surface in an SO ₄ aqueous solution and anodized with direct current so that the weight of the anodized film is 2.5 g / m ² at a current density of 2 A / dm ² , and a substrate is prepared. did. ◆ Roughening treatment F While supplying an aluminum plate with a suspension of pumice and water having an average particle size of about 15 to 35 μm on the aluminum surface,
Brush graining treatment was performed with a rotating nylon brush having a bristle diameter of 0.570 mm and a bristle length of 90 mm. Then, using a 26% aqueous solution of sodium hydroxide and a 6.5% aluminum ion solution, a spray etching treatment was performed at a liquid temperature of 75 ° C. so that the etching amount was 15 g / m ² . Then 1
% Nitric acid aqueous solution (containing 0.5% aluminum ion) at 60 ° C. for 10 minutes for desmutting treatment. Then, an electrochemical graining treatment was performed under the following conditions. 1% nitric acid aqueous solution (containing 0.5% aluminum ion) was used as the electrolyte, and the time (TP) between the current value reaching 0 and the peak was 2 msec.
Using a trapezoidal rectangular wave with a ratio of 1: 1 and a carbon electrode as a counter electrode, the average current density of the aluminum anode was 27 A / dm ² (the ratio of the current density of the aluminum anode to the cathode was 1: 0.9.
5), average amount of electricity at aluminum anode 230 coulomb / d
The electrolytic surface-roughening treatment was performed so as to obtain m ² . Then, using a 26% aqueous solution of sodium hydroxide and a 6.5% aluminum ion solution, a spray etching treatment was performed at a liquid temperature of 45 ° C. so that the total etching amount including smut was 0.7 g / m ² . Subsequently, desmutting treatment was performed by spraying with a 25% nitric acid aqueous solution (containing 0.3% of aluminum ions) at 60 ° C. for 10 seconds. Then, 20% H ₂ S
In O ₄ aqueous solution, by placing the cathode against grained surface, an anodized film weight at a current density of 2A / dm ² is 2.
A substrate was prepared by anodizing with direct current so as to obtain 5 g / m ² . ◆ Roughening treatment G Aluminum plate is 10% sodium hydroxide at 50 ° C for 2
After soaking for 0 second, degreasing and etching, it was washed with running water, neutralized with a 25% sulfuric acid aqueous solution for 20 seconds, and washed with water. After that, using a 1% nitric acid aqueous solution (containing 0.5% of aluminum ions), a trapezoidal rectangular wave with a frequency (Hz) of 2 msec and a frequency ratio of 60 Hz and a duty ratio of 1: 1 was used. Using a carbon electrode as a counter electrode, the average current density at the time of aluminum anode is 27 A / dm ² (the ratio of the current density at the time of anode and cathode of aluminum is 1: 0.9
5), average quantity of electricity 270 coulomb / d for aluminum anode
The electrolytic surface-roughening treatment was performed so as to obtain m ² . After immersing in a 5% aqueous solution of sodium hydroxide (containing 1.5% of aluminum ions) for 7 seconds at 35 ° C. to perform etching (0.07 g / m ^{2 in} terms of the amount of pure aluminum dissolved), rinse with running water and then 2
The mixture was neutralized and washed with a 5% sulfuric acid aqueous solution and washed with water. Then 20%
In H ₂ SO ₄ aqueous solution, by placing the cathode in grained surface, an anodized film weight at a current density of 2A / dm ² is 2.
A substrate was prepared by anodizing with direct current so as to obtain 5 g / m ² . ◆ Roughening treatment F Aluminum plate is 10% sodium hydroxide at 50 ℃ for 2
After soaking for 0 second, degreasing and etching, it was washed with running water, neutralized with a 25% sulfuric acid aqueous solution for 20 seconds, and washed with water. After that, using a 1% hydrochloric acid aqueous solution (containing 0.5% aluminum ions), a trapezoidal rectangular wave with a frequency (60 Hz) of 2 msec and a duty ratio of 1: 1 between the current value reaching 0 and the peak value Using a carbon electrode as a counter electrode, the average current density at the time of aluminum anode is 27 A / dm ² (the ratio of the current density at the time of anode and cathode of aluminum is 1: 0.9
5), average electricity quantity at aluminum anode 350 coulomb / d
The electrolytic surface-roughening treatment was performed so as to obtain m ² . Then, using a 26% aqueous solution of sodium hydroxide and a 6.5% aluminum ion solution, a spray etching treatment was performed at a liquid temperature of 45 ° C. so that the total etching amount including smut was 0.7 g / m ² . Subsequently, desmutting treatment was carried out by spraying treatment at 60 ° C. for 10 seconds with a 25% nitric acid aqueous solution (containing 0.3% of aluminum ions). After that, 20% H ₂ SO
_{4 In an} aqueous solution, place the cathode on the grained surface, and the current density is 2 A / dm ² , the weight of the anodic oxide film is 2.5 g / m ²
To produce a substrate.

[Preparation] [Preparation] A A ₂ Na.3SiO ₂ aqueous solution was immersed in an aqueous solution of Na ₂ O · 3SiO ₂ for 15 seconds for silicate treatment, then washed with water and dried. [Preparation B] Vapor sealing treatment was performed for 10 seconds in a saturated steam chamber at 100 ° C and 1 atm. [Preparation] C 1% Alkyl Glucoxide (alkyl group is C ₁₀ ) aqueous solution was immersed at 50 ° C. for 30 seconds, washed with water and dried. [Preparation Treatment D] After being immersed in a 5% aqueous sodium hydrogen sulfate solution at 85 ° C. for 1 minute, it was washed with water and dried. ◆ Pretreatment E After immersion treatment in a 0.01% NaOH aqueous solution at 95 ° C. for 1 minute, it was washed with water and dried. [Preparation] F 1% sodium nitrite aqueous solution was treated at 80 ° C. for 1 minute, then 0.005% CMC aqueous solution was similarly treated, and then dried. [Preparation Treatment G] After being immersed in a 0.01% sodium acetate aqueous solution at 85 ° C. for 30 seconds, it was dried at 80 ° C. for 5 minutes. [Preparation] H After dipping treatment in an aqueous solution containing 10% sodium dihydrogen phosphate dihydrate and 0.1% sodium fluoride at 65 ° C. for 30 seconds, it was washed with water and dried.

[Undercoat] ◆ Undercoat A Undercoat solution Triethanolamine hydrochloride 0.5 g Methanol 95 g Water 5 g Drying conditions 80 ° C., 30 seconds. Undercoat B Undercoat solution β-alanine 0.5 g Methanol 95 g Water 5 g Drying conditions 80 ° C., 30 seconds. Undercoat C Undercoat liquid Phenylphosphonic acid 0.1 g Vapor sealing 10% Sulfuric acid 1.2 g Methanol 70 g Pure water 30 g Drying conditions 80 ° C., 30 seconds. ◆ Undercoat D Undercoat liquid Aminoethylphosphonic acid 0.10 g Phenylphosphonic acid 0.15 g β-alanine 0.10 g Methanol 40 g Pure water 60 g Drying conditions 80 ° C., 30 seconds.

[Backcoat] The following sol-gel reaction solution was applied with a bar coater and dried at 100 ° C. for 1 minute to prepare a substrate provided with a backcoat layer having a coating amount of 50 mg / m ² after drying. . Sol-gel reaction solution Tetraethyl silicate 50 parts by weight Water 21.6 parts by weight Methanol 10.8 parts by weight Nitric acid 0.05 parts by weight When the above components were mixed and stirred, heat was generated in about 5 minutes. 10
After reacting for minutes, 700 parts by weight of methanol was added to prepare a back coat coating solution.

[0122]

[Coating of photosensitive layer and matte layer]

Photosensitive layer A: The following coating liquid was applied to the support so that the dry weight was 2 g / m ² . Esterified product of 1,2-diazonaphthoquinone-5-sulfonyl chloride and pyrogallol-acetone resin (weight average molecular weight 2500) 40 parts by weight Phenol formaldehyde resin (weight average molecular weight 10000, 90% of trinuclear or more components 90%) 75 parts by weight acrylic Polymer I ^* 35 parts by weight 2- (p-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine 3 parts by weight Oil Blue # 603 (manufactured by Orient Chemical Industry Co., Ltd.) 1.5 parts by weight Mega Fuck F-176 (Fluorine-based surfactant manufactured by Dainippon Ink and Chemicals, Inc.) 0.3 parts by weight Methyl ethyl ketone 1000 parts by weight Propylene glycol monomethyl ether 1000 parts by weight * Acrylic polymer I

[0123]

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60.3 g of N- (p-toluenesulfonyl) methacrylamide, 10.0 g of acrylonitrile and 46.0 g of ethyl acrylate were dissolved in 232.6 g of dimethylformamide, and 2,2'-azobis (2,2 'was dissolved under a nitrogen stream. 4-dimethylvaleronitrile) 0.224 g
Was used as a polymerization initiator, and the mixture was stirred at 65 ° C. for 7 hours. The reaction solution was allowed to cool and then reprecipitated in 5 liters of water. The precipitated polymer was collected by filtration and dried to obtain 110.4 g of acrylic polymer I (yield 95%, Mw 52,000). Further, the following mat forming resin liquid was sprayed to form a mat layer. A 12% aqueous solution of a methyl methacrylate / ethyl acrylate / acrylic acid (preparation weight ratio 65:20:15) copolymer as a part of sodium salt was prepared as a mat layer forming resin liquid, and a rotary atomizing electrostatic coating machine was prepared. The atomizing head rotation speed is 25,000 rpm, and the amount of resin liquid sent is 4
0 ml / min, the applied voltage to the atomizing head was -90 kV, the ambient temperature during application was 25 ° C, and the relative humidity was 50%.
The coated surface was sprayed with steam for 5 seconds to wet it, and 3 seconds after wetting, a temperature of 60 ° C. and a humidity of 10% was sprayed for 5 seconds to dry. Photosensitive layer B: The following coating liquid was applied and dried at 100 ° C. for 1 minute to obtain a coating amount of 1.8 g / m ² . Esterification product of 1,2-diazonaphthoquinone-5-sulfonyl chloride and pyrogallol-acetone resin (weight average molecular weight 3000) 45 parts by weight Phenol formaldehyde resin (weight average molecular weight 12000, 95% of trinuclear or higher component 95%) 84 parts by weight acrylic Polymer II ^* 36 parts by weight Naphthoquinone diazide-1,2-diazide-4-sulfonic acid chloride 1 part by weight Tetrahydrophthalic anhydride 2 parts by weight Benzoic acid 1 part by weight 4- [p-N, N-bis (ethoxycarbonylmethyl) Aminophenyl] -2,6-bis (trichloromethyl) -s-triazine 2 parts by weight Victoria Pureable-BOH (manufactured by Hodogaya Chemical Co., Ltd.) Dye in which the counter anion is changed to 1-naphthalenesulfonic acid 3.5 Weight part Megafac F-177 (Dainippon Ink and Chemicals ( Co., Ltd. 0.8 parts by weight Methyl ethyl ketone 1250 parts by weight Propylene glycol monomethyl ether 500 parts by weight * Acrylic polymer II

[0125]

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The synthetic method was according to Acrylic Polymer I, and 2,2'-azobis (2,4-dimethylvaleronitrile) was used as a polymerization initiator under a nitrogen stream. The matte layer was provided similarly to the case of the photosensitive layer A. Photosensitive layer C: The following coating liquid was provided so that the dry weight was 1.8 g / m ² . Esterification product of 1,2-dianaphthoquinone-5-sulfonyl chloride and pyrogallol-acetone resin (weight average molecular weight 3000) 35 parts by weight Phenol formaldehyde resin (weight average molecular weight 13000, 95% or more of nuclide component 95%) 80 parts by weight methacryl Copolymer of acid (26 mol%): methyl methacrylate (74 mol%) (≡ acrylic polymer III) (weight average molecular weight 45,000) 15 parts by weight 2- (p-methoxyphenyl) -4,6-bis (Trichloromethyl) -s-triazine 2.5 parts by weight Crystal Violet 1 part by weight Oil Blue # 603 1 part by weight Ethylene dichloride 1200 parts by weight 2-Methoxyethyl ascerate 800 parts by weight Megafac F-176 (Dainippon Ink and Chemicals) Industrial Co., Ltd. 0.6 parts by weight Matte layer is photosensitive It was provided as in Layer A. Photosensitive layer D: The following coating liquid was provided on the support so that the dry weight was 10 g / m ² . Esterification product of 1,2-diazonaphthoquinone-5-sulfonyl chloride and pyrogallol-acetone resin (weight average molecular weight 2500) 45 parts by weight Phenol formaldehyde resin (weight average molecular weight 12000, 90% or more of trinuclear or more components) 95 parts by weight Acrylic polymer II (same as photosensitive layer B) 12.5 parts by weight Acrylic polymer III (same as photosensitive layer C) 12.5 parts by weight Naphthoquinonediazide-1,2-diazide-4-sulfonic acid chloride 1 part by weight Tetrahydrophthalic anhydride Acid 2 parts by weight 4- [p-N, N-bis (ethoxycarbonylmethyl) aminophenyl] -2,6-bis (trichloromethyl) -s-triazine 1 part by weight Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) 3 parts by weight Megafac F-176 (Dainippon Ink and Chemicals) Ltd.)) 0.6 parts by weight Methyl ethyl ketone 1400 parts by weight of propylene glycol monomethyl ether 600 parts by weight mat layer was formed as in the case of the photosensitive layer A. Photosensitive layer E: The following coating solution was coated on a support so that the dry weight was 2 g / m ² . Esterification product of 1,2-diazonaphthoquinone-5-sulfonyl chloride and pyrogallol-acetone resin (weight average molecular weight 2500) 30 parts by weight 1,2-diazonaphthoquinone-5-sulfonyl chloride and 2,3,4-trihydroxybenzophenone Esterification (esterification rate 90%) 15 parts by weight Phenome formaldehyde resin (weight average molecular weight 12000, 90% of trinuclear or higher component 90%) 95 parts by weight Acrylic polymer I (same as photosensitive layer A) 25 parts by weight 2-trichloro Methyl-5- [β- (2-benzofuryl) vinyl] -1,3,4-oxadiazole 2 parts by weight Phthalic anhydride 2 parts by weight Naphthoquinone diazide-1,2-diazide-4-sulfonic acid chloride 1 part by weight Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) 3 parts by weight F C-43D (Sumitomo 3M) 0.5 parts by weight Ethyl cellosolve 2000 parts by weight The matte layer was provided in the same manner as in the case of the photosensitive layer A. Photosensitive layer F: Prepare the following photosensitive solution, apply it on the previously grained substrate so that the dry weight is 1.5 g / m ^2, and dry at 80 ° C. for 2 minutes to obtain a negative film. Type PS
Got the edition. Photosensitive solution Methyl methacrylate / N- [6- (methacryloyloxy) hexyl] -2,3-dimethylmaleimide / methacrylic acid = 10/60/30 (molar ratio) copolymer [Mw = 3.5 × 10 ⁴ (GPC), Tg = about 40 ° C. (DSC)] 5 parts by weight 3-ethoxycarbonyl-7-methyl-thioxanthone 0.25 parts by weight Dodecylbenzenesulfonate of a formaldehyde co-condensate of 4-diazodiphenylamine and phenoxyacetic acid 0.20 parts by weight Propylene glycol monomethyl ether 50 parts by weight Methyl ethyl ketone 50 parts by weight Megafac F-177 (Dainippon Ink and Chemicals, Inc., fluorine-based nonionic surfactant) 0.03 parts by weight Victoria Pure Blue BOH Tsuchiya Chemical Industry Co., Ltd.) 0.10 parts by weight ◆ Photosensitive layer G: coating below Solution was applied to the support as a dry weight 2 g / m ² body. Esterification product of 1,2-diazonaphthoquinone-5-sulfonyl chloride and pyrogallol-acetone resin 20 parts by weight Esterification product of 1,2-diazonaphthoquinone-5-sulfonyl chloride and 2,3,4-trihydroxybenzophenone (esterification rate 90%) 15 parts by weight Phenome formaldehyde resin (weight average molecular weight 12000, 90% of trinuclear or higher component 90%) 40 parts by weight Acrylic polymer IV ^* 90 parts by weight 2-trichloromethyl-5- [β- (2-benzofuryl)) Vinyl] -1,3,4-oxadiazole 1 part by weight Phthalic anhydride 2 parts by weight Naphthoquinone diazide-1,2-diazide-4-sulfonic acid chloride 1 part by weight Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) ) 3 parts by weight FC-430 (Sumitomo 3M) 0.5 parts by weight Chill ethyl ketone 800 parts by weight Propylene glycol monomethyl ether 400 parts by weight γ-butyrolactone 600 parts by weight * Acrylic polymer IV

[0127]

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The synthetic method was according to Acrylic Polymer I, and 2,2'-azobis (2,4-dimethylvaleronitrile) was used as a polymerization initiator under a nitrogen stream. The matte layer was provided as in the case of the photosensitive layer A. Photosensitive layer H: The following coating solution was provided on the support so that the dry weight was 1.8 g / m ² . Esterification product of 1,2-diazonaphthoquinone-4-sulfonyl chloride and cresol resin (weight average molecular weight 3000) 35 parts by weight Phenol formaldehyde resin (weight average molecular weight 10000, 90% of components having 3 or more nuclei) 70 parts by weight Acrylic polymer II (Same as the photosensitive layer B) 40 parts by weight 2- (p-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine 3 parts by weight Oil Blue # 603 (manufactured by Orient Chemical Industry Co., Ltd.) 1 , 5 parts by weight Megafac F-176 (Dainippon Ink and Chemicals Co., Ltd. fluorinated surfactant) 0.3 parts by weight Methyl ethyl ketone 1000 parts by weight Propylene glycol monomethyl ether 1000 parts by weight Matte layer in case of photosensitive layer A The same as above.

The PS plate thus prepared was exposed for 60 seconds through a document film from a distance of 1 m using a 3 kW metal halide lamp.

[0130]

[Developer and Development Treatment] ◆ Developer a (pH about 12.4) D-sucrose 4.8% by weight sodium hydroxide 0.34% by weight sodium carbonate 0.70% by weight tetrabutylammonium bromide 0.03% by weight Water 94.7 wt% Development replenisher a (pH about 13.0) D-saccharose 9.7 wt% Sodium hydroxide 1.5 wt% Sodium carbonate 1.0 wt% Tetrabutylammonium bromide 0.07 wt% Water 87.7% by weight Developer b (pH about 12.4) Reduced starch syrup (70% aqueous solution, Amamine 500, manufactured by Kyowa Hakko Kogyo Co., Ltd.) 11.3% by weight Sodium hydroxide 0.40% by weight Polyoxyethylene (25 moles added) Diglyceryl ether 0.03% by weight Water 88.1% by weight Development replenisher b (pH about 13.2) Reduced starch syrup (70% aqueous solution, brand name Amamine 500, manufactured by Kyowa Hakko Kogyo Co., Ltd.) 11.3% by weight Sodium hydroxide 1.6% by weight Polyoxyethylene (25 moles added) Diglyceryl ether 0.07% by weight Water 87.0% by weight Developer c (pH about 12.4) D-saccharose 4.8% by weight Sodium hydroxide 0.34% by weight Sodium carbonate 0.70% by weight Polyoxyethylene (25 moles added) Di Glyceryl ether 0.05% by weight Water 95.26% by weight Development replenisher c (pH about 13.0) D-saccharose 9.7% by weight Sodium hydroxide 1.5% by weight Sodium carbonate 1.0% by weight Polyoxy Ethylene (25 moles added) Diglyceryl ether 0.07% by weight Water 94.4% by weight Developer d (pH about 12.8) D-sol Vitol 5.1% by weight Sodium hydroxide 1.0% by weight Polyoxyethylene adduct of ethylenediamine (Ethylene oxide addition mole number 30) 0.05% by weight Water 93.8% by weight Development replenisher d (pH about 13. 5) D-sorbitol 5.1% by weight sodium hydroxide 2.3% by weight Polyoxyethylene adduct of ethylenediamine (ethylene oxide addition mole number 30) 0.07% by weight water 92.5% by weight ◆ Developer e (pH) About 12.7) [SiO ₂ ] / [Na ₂ O] molar ratio 1.3, SiO ₂ 1.4 wt% sodium silicate aqueous solution 100 parts by weight Polyoxyethylene (25 moles added) Diglyceryl ether 0.05 parts ◆ replenisher e (pH about 13.6) [SiO _2] / [Na ₂ O] molar ratio 1.1, SiO ₂ 1.4 wt% of silicate sodium Aqueous solution of water 100 parts by weight Polyoxyethylene (25 moles added) Diglyceryl ether 0.07 parts by weight Developer f (pH 12.3) [SiO ₂ ] / [Na ₂ O] molar ratio 1.7, SiO ₂ 1 .4% by weight aqueous sodium silicate solution 100 parts by weight Polyoxyethylene adduct of ethylenediamine (ethylene oxide addition mole number 30) 0.03 parts by weight Development replenisher f (pH about 13.3) [SiO ₂ ] / [Na ₂ O] molar ratio of 1.2, SiO ₂ 1.4 wt% sodium silicate aqueous solution 100 parts by weight Polyoxyethylene adduct of ethylenediamine (ethylene oxide addition mole number 30) 0.03 parts by weight

[Finishing gum solution] Gum arabic 1.8% by weight Enzyme-modified potato starch 18.3% by weight Enzyme-modified egg candy starch starch 3.7% by weight Phosphorylated waxy eggplant starch starch 1.8% by weight Dioctyl sulfosuccinate sodium salt 0.91% by weight Ammonium monophosphate 0.27% by weight Phosphoric acid (85%) 0.37% by weight EDTA-tetrasodium salt 0.27% by weight Ethylene glycol 1.8% by weight Benzyl alcohol 2.3% by weight Dehydroacetic acid Sodium 0.04% by weight Emulsion type antifoaming agent 0.02% by weight Water 68.4% by weight

[Rinse Solution] Sodium dodecyl diphenyl ether disulfonate (40% by weight aqueous solution) 6.7% by weight Sodium hexametaphosphate 0.8% by weight Benzyl alcohol 1.5% by weight Polyoxyethylene (12 mol of ethylene oxide added) Nonylphenyl ether 1.5 wt% Sodium dioctyl sulfosuccinate 1.4 wt% Phosphoric acid (85 wt%) 5.2 wt% Sodium hydroxide 2.0 wt% Silicon antifoam 0.01 wt% Water 80.89 wt%

[Process 1] Next, a commercially available automatic processor PS-900D (Fuji Photo Film Co., Ltd.) having an immersion type developing tank is used.
20 liters of each developer described above is charged into a developing tank of
The temperature was kept at 30 ° C. The second bath of PS-900D has 8 liters of tap water, and the third bath has finishing liquid: water =
8 liters of a 1: 1 diluted finishing solution was charged. The PS-900D prepared in this way was passed through the above-mentioned exposed PS plate and developed. At this time, using a step tablet (15 steps with an optical density difference of 0.15 in one step), the quantity of light is changed stepwise to develop what is printed on the PS plate at the same time, and the light quantity on the plate is increased. Read the number of steps (clear / solid steps) of the remaining image corresponding to
The value was defined as the sensitivity when the PS plate was developed with each developing solution, and the above developing replenishers were replenished so that the sensitivity remained constant during the processing. The lithographic printing plate obtained under such conditions was set on an offset printing machine Sprint 25 (manufactured by Komori Printing Co., Ltd.), and printing results are shown in Table 1) to
It is shown in Table 23). [Processing 2] Similarly, 20 liters of each of the above developing solutions was placed in a developing tank of a commercially available automatic processor PS-900D (manufactured by Fuji Photo Film Co., Ltd.) having an immersion type developing tank and kept at 30 ° C. 8 liters of the above rinse solution 1: water = 1: 7 diluted rinse solution was charged in the second bath of PS-900D, and 8 liters of the same diluted rinse solution was charged in the third bath. The PS-900D prepared in this way was passed through the above-mentioned exposed PS plate and developed. At this time, step tablet (1
(15 steps with an optical density difference of 15 steps with a step difference of 0.15) is used to simultaneously develop what is printed on the PS plate by gradually changing the light quantity, and the image remaining corresponding to the light quantity on the plate is developed. Read the number of stages (clear / solid number) and set the value to P
It is defined as the sensitivity when developed with each S plate developing solution, and the above developing replenishers were replenished so that this sensitivity remained constant during processing. Also, at this time, the rinse diluted solution in the third bath is 30 ml /
m ^{2 was} replenished, and the overflow solution was transferred to the second bath for use. A lithographic printing plate obtained under such conditions is offset printing machine Sprint 25 (manufactured by Komori Printing Co., Ltd.)
The results of printing and setting on are set forth in Tables 1) to 23).

[0134]

[Table 1]

[0135]

[Table 2]

[0136]

[Table 3]

[0137]

[Table 4]

[0138]

[Table 5]

[0139]

[Table 6]

[0140]

[Table 7]

[0141]

[Table 8]

[0142]

[Table 9]

[0143]

[Table 10]

[0144]

[Table 11]

[0145]

[Table 12]

[0146]

[Table 13]

[0147]

[Table 14]

[0148]

[Table 15]

[0149]

[Table 16]

[0150]

[Table 17]

[0151]

[Table 18]

[0152]

[Table 19]

[0153]

[Table 20]

[0154]

[Table 21]

[0155]

[Table 22]

[0156]

[Table 23]

Claims (1)

[Claims] 1. A compound containing at least one compound selected from silicic acid, phosphoric acid, carbonic acid, boric acid, phenols, sugars, oximes and fluorinated alcohols and having a pH of 1.
A method of developing a photosensitive lithographic printing plate, which comprises developing with an alkaline aqueous solution having a range of more than 2.0 and less than 13.0.