JP3537536B2 - Manufacturing method of photosensitive lithographic printing plate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a manufacturing <br/> production method of the photosensitive lithographic printing plate.

[0002]

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

In such a positive photosensitive lithographic printing plate, when the photosensitive layer is subjected to image exposure and then developed, the photosensitive layer which is ink-receptive at the exposed portion is removed and the surface of the hydrophilic support is exposed. On the other hand, the non-exposed portions of the ink-receiving photosensitive layer remain on the support to form an ink-receiving layer. In lithographic printing, the difference in the property that the exposed portion is hydrophilic and the unexposed portion is lipophilic is used.

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

A photosensitive composition using trihydroxybenzophenone-1,2-naphthoquinonediazidosulfonic acid ester and a cresol formaldehyde novolak resin, which is the most typical example of these photosensitive compositions, is disclosed in Thompson "Introduction to Micro". Lithography "(ACS Publishing, No. 219, pp 112-121), and U.S. Patent No. 3,666,473,
U.S. Pat.No. 4,115,128 and U.S. Pat.No.4,173,470
Patent Documents and the like describe those having a naphthoquinonediazide-substituted compound and a novolak-type phenol resin which is an alkali-soluble resin. In addition, photosensitive compositions containing many naphthoquinonediazide compounds and alkali-soluble resins have been proposed and put to practical use.

The orthoquinonediazide compound generates a carboxylic acid upon irradiation with actinic light and becomes soluble in an aqueous alkali solution. By utilizing this property, a photosensitive composition containing these naphthoquinonediazide compound and an alkali-soluble resin was used. For the plate making process of a positive photosensitive lithographic printing plate,
An aqueous alkaline developer is used.

In order to enhance the developability of a photosensitive lithographic printing plate, it is necessary to increase the alkali solubility of the photosensitive composition. As a method for increasing the alkali solubility, an alkali-soluble resin which reduces the molecular weight of a naphthoquinonediazide photosensitive material is used. It is known to reduce the molecular weight of the photosensitive layer in the photosensitive layer, or to add an organic acid, an inorganic acid, or an acid anhydride.However, this method deteriorates the film strength. In addition, problems such as a decrease in printing durability and a narrow range of appropriate developing conditions occur.

Japanese Patent Application Laid-Open No. 58-205154 discloses a photosensitive lithographic printing plate which solves the above-mentioned problems, in which a support is provided with a photosensitive layer comprising an upper layer and a lower layer, and an o-quinonediazide compound in the upper layer is provided. A photosensitive lithographic printing plate in which the content is larger than the content of the o-quinonediazide compound in the lower layer is described. Although this photosensitive lithographic printing plate does solve some of the above problems, it is still
Since it is not sufficient, and it is an essential requirement to form an upper layer and a lower layer, the production process is complicated and the production cost is unavoidable.

Therefore, the present inventors have studied and found that the concentration distribution of the o-quinonediazide compound in the photosensitive layer is as follows.
It has been found that the above problem can be solved by setting the maximum concentration of the o-quinonediazide compound at a position farther than 1/2 of the thickness of the photosensitive layer as viewed from the support side.

[0010]

OBJECTS OF THE INVENTION Accordingly, an object of the present invention has a wide range of fitness development conditions, and without deterioration of the film strength, a sufficient printing durability, also the sensitive photosensitive lithographic printing plate It is to provide a manufacturing method.

[0011]

SUMMARY OF THE INVENTION The object of the present invention is to provide a photosensitive lithographic printing plate comprising at least one photosensitive layer containing an o-quinonediazide compound and an alkali-soluble resin on a support. -A method for producing a photosensitive lithographic printing plate, characterized in that the maximum concentration of the quinonediazide compound is located at a position farther than 1/2 of the thickness of the photosensitive layer when viewed from the support side, wherein the o-quinonediazide compound is at room temperature. Conversion
One solvent capable of dissolving at least 5% by weight of the compound,
It has a boiling point 20 ° C or more higher than that of one solvent, and
Less than 5% by weight of o-quinonediazide compound
A coating solution obtained by dissolving a photosensitive composition containing an o-quinonediazide compound and an alkali-soluble resin in a mixed solvent with a certain other solvent is applied to a support, and a low-temperature, high-temperature,
The low intermediate temperature at three different intermediate temperature conditions.
The method can be achieved by a method for producing a photosensitive lithographic printing plate characterized by drying in the order of temperature, the intermediate temperature, and the high temperature .

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

The support preferably has a flexibility that can be set in an ordinary printing press and withstands a load applied during printing. For example, a metal plate of aluminum, magnesium, zinc, chromium, iron, copper, nickel, or the like; An alloy plate of these metals, a metal plate coated with chromium, zinc, copper, nickel, aluminum, iron, or the like by plating or vapor deposition can be used. Of these, those which are preferable as the support are those using aluminum or an alloy thereof.

Various aluminum alloys can be used, for example, silicon, copper, manganese, magnesium,
An alloy of aluminum with a metal such as chromium, zinc, lead, bismuth, and nickel can be used.

A support made of aluminum or an alloy thereof is generally subjected to a degreasing treatment prior to graining treatment in order to remove grease components such as rolling oil adhering to the surface of the support. Examples of the degreasing treatment include a degreasing treatment using a solvent such as trichlene and thinner, and an emulsion degreasing treatment using an emulsion of kesilon and triethanol. In the degreasing treatment, an aqueous solution of an alkali such as caustic soda can also be used. When an aqueous solution of an alkali such as caustic soda is used for the degreasing treatment, dirt and an oxide film which cannot be removed only by the above degreasing treatment can be removed.

The graining treatment of the present invention includes a so-called mechanical surface roughening method for mechanically roughening the surface, a so-called chemical surface roughening method for chemically dissolving and roughening the surface, and an electrochemical method. A known method such as a so-called electrochemical surface roughening method for uniformly roughening the surface can be used.

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

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

Since a smut is formed on the surface of the support obtained by the graining treatment, it is generally preferable to appropriately perform a treatment such as washing with water or alkali etching to remove the smut. Examples of such a treatment include a treatment method such as an alkali etching method described in JP-B-48-28123 and a desmut sulfate method described in JP-A-53-12739.

The support treated as described above is then subjected to an anodic oxidation treatment. Wear resistance due to anodizing treatment,
Chemical resistance and water retention can be improved. A known method can be used for the anodizing treatment. For example, a method in which an aqueous solution containing sulfuric acid and / or phosphoric acid at a concentration of 10 to 50% is used as an electrolytic solution at a current density of 1 to 10 A / dm ² is used. Although preferably used, a method of electrolyzing at a high current density in sulfuric acid described in U.S. Patent No. 1,412,768, and a method of electrolyzing using phosphoric acid described in U.S. Patent No. 3,511,661 Etc. can also be used.

The anodized support may be subjected to a sealing treatment as required. These sealing treatments can be performed using a known method such as hot water treatment, boiling water treatment, steam treatment, sodium silicate treatment, dichromate aqueous solution treatment, nitrite treatment, and ammonium acetate treatment.

The support is preferably further provided with a hydrophilic layer. For the formation of the hydrophilic layer, a water-soluble polymer, an alkali metal silicate described in U.S. Patent No. 3,181,461,
JP-A-60-149949, amino acids and salts thereof described in JP-A-63-165183, amines having a hydroxyl group and salts thereof described in JP-A-60-232998, 1
Phosphate described in 9494, a polymer compound containing a monomer unit having a sulfo group described in JP-A-59-101651, and the like can be used.In the present invention, the following compounds are used. Is preferred. Specific examples of the water-soluble polymer include vinyl resins such as PVA (polyvinyl alcohol), modified PVA, PVPA (polyvinyl phosphonic acid), polyvinyl pyrrolidone, and polyvinyl imidazoline and derivatives thereof; polyacrylic acid, polyacrylamide, and polyhydroxyethyl acrylate. Acrylic acid-based copolymers such as polyethyleneimine; maleic acid copolymer; polyethylene glycol; polypropylene glycol; polyurethane resin;
Polyhydroxymethylmelamine resin; soluble starch;
CMC (carboxymethylcellulose); hydroxyethylcellulose; guar gum; tragacanth gum; xanthan gum; sodium alginate; At least one amino group and two or more

[0023]

Embedded image A compound having a selected group or a salt thereof Examples of the compound having a phosphonic acid group or a salt thereof include 1-aminoethane-1,1-diphosphonic acid and 1-amino-1-phenylmethane-1,1 -Diphosphonic acid, 1-dimethylaminoethane-1,1-diphosphonic acid, 1-dimethylaminobutane-1,1-diphosphonic acid, 1-dimethylaminomethane-1,1-diphosphonic acid, 1-propylaminoethane-1 , 1-diphosphonic acid, 1-butylaminomethane-1,1-diphosphonic acid,
Aminotrimethylenephosphonic acid, ethylenediaminopentamethylenephosphonic acid, ethylenediaminotetramethylenephosphonic acid, diethylenetriaminopentamethylenephosphonic acid, aminotri (2-propylene-2-phosphonic acid), and hydrochloride, formate, and oxalates of these compounds Examples of the compound having a phosphinic acid group or a salt thereof include compounds in which the phosphonic acid group of the compound having a phosphonic acid group is changed to a phosphinic acid group or salts of these compounds, for example, aminotrimethylene. Examples of the compound having a phosphoric acid group or a salt thereof include compounds in which the phosphonic acid group of the compound having a phosphonic acid group is changed to a phosphoric acid group, and salts of these compounds.
For example, aminotrimethylene phosphoric acid and the like can be mentioned. Compounds having at least one amino group and a carboxyl group or a sulfone group or salts thereof include aminoacetic acid, lysine, threonine, serine, aspartic acid, parahydroxyphenylglycine, dihydroxyethylglycine, anthranilic acid, tryptophan, Examples include amino acids such as arginine, aliphatic aminosulfonic acids such as sulfamic acid and cyclohexylsulfamic acid, and hydrochlorides, formates and oxalates of these compounds. Examples of the compound having at least one amino group and at least one hydroxyl group or a salt thereof include monoethanolamine, diethanolamine, trimethanolamine, tripropanolamine, triethanolamine, and hydrochloride and formate of those compounds. Oxalate and the like. Alkanes having at least two amino groups or their salt alkanes include straight-chain, branched and cyclic ones.

Particularly preferred are NH ₂ — (CH ₂ ) _n
—NH ₂ (n represents an integer of 2 to 10).

As specific examples, ethylenediamine, 1,
3-diaminopropane, 1,4-diaminobutane, 1,
2-diaminopropane, 1,2-diamino-2-methylpropane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,2-diaminocyclohexane, 1,8-diaminooctane , 1,
Examples include 9-diaminononane, 1,10-diaminodecane, and hydrochloride, formate, and oxalate salts of these compounds.

Next, the o-quinonediazide compound and the alkali-soluble resin used in the photosensitive layer of the photosensitive lithographic printing plate of the present invention will be described.

The o-quinonediazide compound used in the photosensitive layer of the present invention is a compound having an o-quinonediazide group in a molecule, and can be used in the present invention.
-Quinonediazide compound is not particularly limited, for example, a polycondensation resin having an orthoquinonediazide group, such as an ester compound of o-naphthoquinonediazidesulfonic acid with a polycondensation resin of phenols and aldehydes or ketones. Can be

Examples of the phenol in the polycondensation resin with the phenol and aldehyde or ketone include, for example, phenol, o-cresol, m-cresol,
Examples include monohydric phenols such as p-cresol, 3,5-xylenol, carvacrol, and thymol; dihydric phenols such as catechol, resorcin, and hydroquinone; and trihydric phenols such as pyrogallol and phloroglucin. As the aldehyde, for example, formaldehyde,
Examples include benzaldehyde, acetaldehyde, crotonaldehyde, and furfural. Preferred among these are formaldehyde and benzaldehyde. Examples of the ketone include acetone, methyl ethyl ketone, and the like.

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

In the above-mentioned o-naphthoquinonediazide compound, the condensation rate of o-naphthoquinonediazidesulfonic acid to OH groups of phenols (reaction rate for one OH group) is preferably 15% to 80%, more preferably 20%. ~
45%.

Further, as the orthoquinonediazide compound used in the present invention, the following compounds described in JP-A-58-43451 can be exemplified. That is, for example, 1,
2-benzoquinonediazidesulfonic acid ester, 1,2
-Naphthoquinonediazidesulfonic acid ester, 1,2-
Known 1,2 such as benzoquinonediazidosulfonic acid amide and 1,2-naphthoquinonediazidosulfonic acid amide
-Quinonediazide compounds, more specifically, "Light-Sensitive Systems" by J. Kosar, 339-352 (196)
5 years), John Willy and Sands
ey & Sons) (New York)
1,2-Benzoquinonediazide-4-sulfonic acid phenyl ester, described in "Photoresist", Volume 50 (1975), McGraw Hill, New York, by WSDe Forest. 1,2,1 ', 2'-di- (benzoquinonediazide-4-sulfonyl) -dihydroxybiphenyl, 1,2-benzoquinonediazide-4- (N-ethyl-N-β-naphthyl) -sulfonamide, , 2-Naphthoquinonediazido-5-sulfonic acid cyclohexyl ester, 1- (1,2-naphthoquinonediazide-5-sulfonyl) -3,5-dimethylpyrazole, 1,2-naphthoquinonediazide-5-sulfonic acid-4'- Hydroxydiphenyl-4′-azo-β-naphthol ester,
N, N-di- (1,2-naphthoquinonediazide-5-sulfonyl) -aniline, 2 '-(1,2-naphthoquinonediazide-5-sulfonyloxy) -1-hydroxy-
Anthraquinone, 1,2-naphthoquinonediazide-5
Sulfonic acid-2,4-dihydroxybenzophenone ester, 1,2-naphthoquinonediazide-5-sulfonic acid-2,3,4-trihydroxybenzophenone ester, 1,2-naphthoquinonediazide-5-sulfonic acid chloride 2 mol and 4 mol Condensate with 1 mol of 4,4'-diaminobenzophenone, 2 mol of 1,2-naphthoquinonediazide-5-sulfonic acid chloride and 4,4'-dihydroxy-
A condensate with 1 mol of 1,1'-diphenylsulfonic acid,
Condensate of 1 mol of 1,2-naphthoquinonediazide-5-sulfonic acid chloride with 1 mol of purpurogallin, 1,2-
Examples thereof include 1,2-quinonediazide compounds such as naphthoquinonediazide-5- (N-dihydroabiethyl) -sulfonamide. In addition, Japanese Patent Publication No. 37-1953
Nos. 37-3627, 37-13109, 40-26126, 40-
No. 3801, No. 45-5604, No. 45-27345, No. 51-13013,
The 1,2-quinonediazide compounds described in JP-A-48-96575, JP-A-48-63802 and JP-A-48-63803 can also be mentioned.

Of the above orthoquinonediazide compounds,
An o-quinonediazide ester compound obtained by reacting 1,2-benzoquinonediazidosulfonyl chloride or 1,2-naphthoquinonediazidosulfonylchloride with a pyrogallol-acetone condensed resin or 2,3,4-trihydroxybenzophenone is particularly preferred.

Next, the alkali-soluble resin will be described.

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

Novolak resins usable in the present invention include, for example, phenol-formaldehyde resin, cresol-formaldehyde resin, and
Phenol-cresol-formaldehyde copolymer resin as described in JP 7841, JP-A-55-12755
Copolymer resins of p-substituted phenol and phenol or cresol and formaldehyde as described in JP-A No. 3 (Kokai) No. 3 are cited.

The molecular weight (polystyrene standard) of the novolak resin preferably has a number average molecular weight Mn of 3.00 × 10 ^{2 to} 7.5.
0 × 10 ³ , weight average molecular weight Mw is 1.00 × 10 ^{3 to} 3.00 × 10 ⁴ ,
More preferably, Mn is 5.00 × 10 ^{2 to} 4.00 × 10 ³ and Mw is 3.
00 × 10 ^{3 to} 2.00 × 10 ⁴ .

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

The novolak resin is used in the photosensitive composition in an amount of from 5 to 95%.
It is preferable that the content be contained by weight.

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

[0040]

Embedded image

In the general formulas [I] to [V], 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,
Preferred is a hydrogen atom or an alkyl group such as a methyl group or an ethyl group. R ₄ and R ₅ represent a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, preferably a hydrogen atom. A represents an optionally substituted alkylene group connecting a nitrogen atom or an oxygen atom to an aromatic carbon atom, m represents an integer of 0 to 10, and B represents a substituent. Represents a phenylene group which may be substituted or a naphthylene group which may have a substituent.

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

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

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

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

As the vinyl polymer having a phenolic hydroxyl group, the above polymers may be used alone or in combination of two or more. Further, it can be used in combination with another polymer compound or the like.

Further, a printout material for forming a visible image upon exposure can be added to the photosensitive layer of the present invention. The printout material is composed of a compound that generates an acid or a free radical upon exposure to light and an organic dye that changes its color by interacting with the generated acid or a free radical. Examples of the compound include, for example, o-naphthoquinonediazide-4-sulfonic acid halogenide described in JP-A-50-36209, trihalomethyl-2-pyrone and trihalomethyl-triazine described in JP-A-53-36223. , JP
O-Naphthoquinonediazide-4 described in JP-A-55-6244
Ester compounds or amide compounds of sulfonic acid chloride with phenols or anilines having an electron-withdrawing substituent, JP-A-55-77742, JP-A-57-148784
And halomethylvinyloxadiazole compounds and diazonium salts described in, for example,
Examples of the organic dye include Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.), Patent Pure Blue (manufactured by Sumitomo Sangoku Chemical Co., Ltd.), and Oil Blue # 603
(Manufactured by Orient Chemical Co., Ltd.), Sudan Blue II
(Manufactured by BASF), crystal violet, malachite green, fuchsin, methyl violet, ethyl violet, methyl orange, brilliant green, congo red, eosin, rhodamine 66 and the like.

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

Further, in order to improve the oil sensitivity of the photosensitive layer, for example, a p-tert-butylphenol formaldehyde resin, a pn-octylphenol formaldehyde resin or these resins may be added to the photosensitive layer of the present invention.
-A resin partially esterified with a quinonediazide compound may be added.

The photosensitive layer of the present invention can be formed by applying a coating solution obtained by dissolving or dispersing a photosensitive composition comprising each of these components in a solvent on a support, followed by drying.

As a coating method used for applying the coating solution for the photosensitive layer on the surface of the support, there are conventionally known methods such as spin coating, wire bar coating, dip coating, air knife coating, spray coating, air spray coating, and the like. Methods such as electrostatic air spray coating, roll coating, blade coating, and curtain coating are used.

[0052] of the present invention, the maximum concentration of o- quinonediazide compound, as viewed from the support side, distantly position than half of the Thickness of the photosensitive layer, o- quinonediazide compound and a photosensitive layer containing an alkali-soluble resin (Hereinafter, referred to as a photosensitive layer of the present invention) comprises an o-quinonediazide compound and
A photosensitive composition containing a potash-soluble resin is reduced in boiling point to o.
The coating solution is formed by applying a coating solution dissolved in a mixed solvent comprising a good solvent of a quinonediazide compound and a poor solvent of an o-quinonediazide compound having a high boiling point, and drying the coating solution at three different temperature conditions.

In the present invention, when a plurality of photosensitive layers are provided, the photosensitive layer on the outermost surface is preferably used as the photosensitive layer of the present invention. Further, a part or all of the plurality of photosensitive layers may be used as the photosensitive layer of the present invention.

The maximum concentration of the o-quinonediazide compound in the photosensitive layer of the present invention is preferably at or near the surface.

The good solvent for the o -quinonediazide compound is
A solvent capable of dissolving the o- quinonediazide compound 5 wt% or more at normal temperature, and a poor solvent of o- quinonediazide compound, a solvent and at room temperature o- quinonediazide compounds may be dissolved less than 5 wt% Say . Further, the difference between the boiling points of the good solvent and the poor solvent is 20 ° C. or more , and more preferably 30 ° C. or more.

A coating solution obtained by dissolving the photosensitive composition in a mixed solvent consisting of a good solvent of an o-quinonediazide compound having a low boiling point and a poor solvent of an o-quinonediazide compound having a high boiling point is applied, and three different temperature conditions are applied. By drying with
Why, although clear not whether the photosensitive layer is formed having a maximum concentration of thickness 1/2 o- quinonediazide compound distant location than the Mi of the photosensitive layer, a low boiling point with the photosensitive composition o-
When a coating solution dissolved in a mixed solvent consisting of a good solvent of a quinonediazide compound and a poor solvent of an o-quinonediazide compound having a high boiling point is applied and dried, a good solvent having a low boiling point and fast evaporation evaporates from the surface, and the photosensitive layer The content of the poor solvent on the surface increases, and the o-quinonediazide compound precipitates with it, and the solution containing the o-quinonediazide compound diffuses therefrom, and the solvent is further evaporated. It is believed that the side can be rich in the o-quinonediazide compound and that the above results will be obtained by performing the drying at three different temperature conditions.

Examples of the good solvent for the o-quinonediazide compound having a low boiling point and the poor solvent for the o-quinonediazide compound having a high boiling point used in the present invention include the following.

Actually, in the present invention, it is only necessary to use a poor solvent for the o-quinonediazide compound having a high boiling point and a good solvent for the o-quinonediazide compound having a low boiling point. Examples of poor solvents for o-quinonediazide compounds having a high boiling point: propylene glycol alkyl ethers (eg, propylene glycol monomethyl ether, propylene glycol monoethyl ether), dipropylene glycol alkyl ethers (eg, dipropylene glycol monomethyl ether, dipropylene glycol) Monoethyl ether), diethylene glycols (eg, dimethyl carbitol (DMDG), diethyl carbitol (DEDG), methyl carbitol), alcohols (eg, pentanol, hexanol, 3-methoxy-1-butanol), methyl propyl Ketone, methyl butyl ketone, diacetone alcohol, cyclopentanone, cyclohexanone. Examples of good solvents for the o-quinonediazide compound having a low boiling point: acetone, methyl ethyl ketone, 4-hydroxy-2-
Butanone, methyl lactate, cellosolves (eg, methyl cellosolve, ethyl cellosolve).

The photosensitive layer of the present invention is dried under three different temperature conditions. It is preferable that drying is performed at a low temperature in the early stage of drying and then at a high temperature. These drying conditions include, for example, the following drying conditions. The combination of drying conditions
The choice can be made by performing simple experiments. The coating amount of the photosensitive layer coating solution is 0.
5 μm to 8.0 μm is preferable, and 1.0 μm to 4.0 μm is more preferable.

The proportion of the o-quinonediazide compound in the photosensitive layer is preferably from 5 to 60% by weight, particularly preferably from 10 to 50% by weight.

In the photosensitive lithographic printing plate of the present invention, the photosensitive layer may have two or more layers.

Further, the o-
The quinonediazide compounds may be the same or different, and the number of o-quinonediazide compounds present in each layer may be plural.

When there are two or more photosensitive layers, at least one of them may be the photosensitive layer of the present invention, the other photosensitive layer may be the photosensitive layer of the present invention, and It may be a photosensitive layer.

The proportion of the o-quinonediazide compound in the photosensitive layer is preferably large in the surface layer.

The coating amount of the photosensitive layer coating solution at this time is preferably 0.5 μm to 8.0 μm, more preferably 1.0 μm to 4.0 μm, as a dry film thickness of the photosensitive layer.

The positive photosensitive lithographic printing plate of the present invention can be made by exposing and developing by a usual method. For example, a transparent original image having a line image, a halftone image, or the like is brought into close contact with the photosensitive surface and exposed, and then a non-image portion of the photosensitive layer is removed with an appropriate developing solution to obtain a relief image. Can be

Light sources suitable for exposure include mercury lamps, metal halide lamps, xenon lamps, chemical lamps,
And carbon arc lamps. Further, as the developer used for the development and the development replenisher, an aqueous alkali solution is preferable. For example, sodium silicate, alkali metal silicates such as potassium silicate, sodium hydroxide, potassium hydroxide, tertiary sodium phosphate, An alkaline aqueous solution such as an aqueous solution of sodium diphosphate, sodium carbonate, potassium carbonate or the like can be used.

In the present invention, the developer used for developing the photosensitive lithographic printing plate and the developing replenisher preferably contain an alkali metal silicate. The alkali metal of the alkali metal silicate includes lithium, sodium and potassium, of which potassium is most preferred.

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

Preferred developers and replenishers are [SiO
₂ ] / [M] (wherein [SiO ₂ ] represents the molar concentration of SiO ₂ and [M] represents the molar concentration of the alkali metal).
Is a 15~1.0, 0.5~5.0 SiO ₂ concentration relative to the total weight
It is an aqueous solution of an alkali metal silicate in weight%. Also, particularly preferably, [SiO ₂ ] / [M] of the developer is
0.25 to 0.75, the SiO ₂ concentration is 1.0 to 4.0% by weight, [SiO ₂ ] / [M] of the developing replenisher is 0.15 to 0.5,
The iO ₂ concentration is 1.0-3.0% by weight.

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

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

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

These water-soluble or alkali-soluble reducing agents can be contained in the developing solution and the developing replenisher at 0.05 to 10% by weight.

Further, the developing agent and the developing replenisher may contain an organic acid carboxylic acid.

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

The lipoprotective carboxylic acids include those having 6 to 20 carbon atoms.
Are preferred, and specific examples thereof include caproic acid, enantiic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, mystyric acid, palmitic acid, and stearic acid. Number 6
~ 12 alkanoic acids. In addition, the aliphatic carboxylic acid,
It may be a fatty acid having a double bond in the carbon chain or a fatty acid having a branched carbon chain. The aliphatic carboxylic acid may be used as a sodium or potassium salt or an ammonium salt.

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

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

The aliphatic carboxylic acid and the aromatic carboxylic acid are used in an amount of 0.
1 to 30% by weight can be contained.

Further, the following anionic, nonionic, and cationic surfactants can be contained in the developer and the development replenisher.

Examples of the anionic surfactant include higher alcohol (C ₆ -C ₂₂ ) sulfates (eg, sodium salt of lauryl alcohol sulfate, sodium salt of octyl alcohol sulfate, ammonium salt of lauryl alcohol sulfate, “@ eepol- 8
1 "(trade name, manufactured by Shell Chemical Co., Ltd., secondary sodium alkyl sulfate, etc.), aliphatic alcohol phosphates (eg, sodium salt of cetyl alcohol phosphate), alkylaryl sulfonates (eg, dodecylbenzene) Sulfonic acid sodium salt, isopropylnaphthalenesulfonic acid sodium salt, dinaphthalene disulfonic acid sodium salt, metanitrobenzenesulfonic acid sodium salt, etc., and alkylamide sulfonates (for example, C ₁₇ H ₃₃ CON)
(CH ₃ ) CH ₂ SO ₃ Na, etc.) and sulfonates of dibasic fatty acid esters (eg, dioctyl sodium sulfosuccinate, dihexyl sodium sulfosuccinate, etc.). Among these, sulfonates are preferably used.

As the nonionic surfactant, either a polyethylene glycol type or a polyhydric alcohol type can be used.

Examples of the nonionic surfactant include, for example,
Examples include compounds represented by the following general formulas [1] to [8].

[0085]

Embedded image In the general formulas [1] to [8], R represents a hydrogen atom or 1
A, b, c, m, n, x, and y each represent an integer of 1 to 40;

The organic group represented by R includes, for example, a linear or branched alkyl group having 1 to 30 carbon atoms, an alkyl group having a substituent [for example, an aryl group (such as phenyl)], and an alkyl moiety. Linear or branched carbon number 1-30
And a phenyl group which may have a substituent (for example, a hydroxyl group or the above-mentioned alkyl group).

Specific examples of the nonionic surfactant are shown below.

Polyethylene glycol, polyoxyethylene lauryl ether, polyoxyethylene nonyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene behenyl ether,
Polyoxyethylene polyoxypropylene cetyl ether, polyoxyethylene polyoxypropylene behenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene stearylamine, polyoxyethylene oleylamine, polyoxyethylene stearamide, Polyoxyethylene oleic acid amide, polyoxyethylene castor oil, polyoxyethylene aviethyl ether, polyoxyethylene lanolin ether, polyoxyethylene monolaurate, polyoxyethylene monostearate, polyoxyethylene glyceryl monooleate, polyoxyethylene Glyceryl monostearate, polyoxyethylene propylene glycol monostearate, oxyethyl Block copolymer, distyrenated phenol polyethylene oxide adduct, tribenzyl phenol polyethylene oxide adduct, octylphenol polyoxyethylene polyoxypropylene adduct, glycerol monostearate, sorbitan monolaurate, polyoxyethylene sorbitan monolaurate, etc. .

The weight average molecular weight of the nonionic surfactant is
A range from 300 to 10,000 is preferred. The concentration of the nonionic surfactant in the developer can be at least 0.001 to 10% by weight.

The cationic surfactant is roughly classified into an amine type and a quaternary ammonium salt type, and any of these can be used.

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

Examples of the quaternary ammonium salt type include a long-chain primary amine salt, an alkyltrimethylammonium salt, a dialkyldimethylethylammonium salt, an alkyldimethylammonium salt, an alkyldimethylbenzylammonium salt, an alkylpyridinium salt, and an alkylpyridinium salt. Norinium salt, alkylisoquinolinium salt, alkylpyridinium sulfate, stearamidomethylpyridinium salt, acylaminoethyldiethylamine salt, acylaminoethylmethyldiethylammonium salt, alkylamidopropyldimethylbenzylammonium salt, fatty acid polyethylene polyamide, acylamino Ethylpyridinium salt, acylcholaminoformylmethylpyridinium salt, stearooxymethylpyridinium salt, fatty acid triethanolamine, fat Acid triethanolamine formate, trioxyethylene fatty acid triethanolamine,
Fatty acid dibutylaminoethanol, cetyloxymethylpyridinium salt, p-isooctylphenoxyethoxyethyldimethylbenzylammonium salt and the like can be mentioned. (“Alkyl” in the examples of the above compounds is a compound having 6 carbon atoms.
Represents -20, linear or partially substituted alkyl,
Specifically, linear alkyl such as hexyl, octyl, cetyl, and stearyl is preferably used. Further, a cationic surfactant of a polymer having a cationic component as a repeating unit, for example, a polymer containing a quaternary ammonium salt obtained by copolymerization with a lipophilic monomer can also be contained.

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

The weight average molecular weight is at least 300 to 500.
A range of 00 can be used.

As the surfactant, it is preferable to use a fluorine-based surfactant containing a perfluoroalkyl group in the molecule. As such a fluorine-based surfactant,
Perfluoroalkyl carboxylate, perfluoroalkyl sulfonate, anionic type such as perfluoroalkyl phosphate, amphoteric type such as perfluoroalkyl betaine, cationic type and perfluoroalkylamine oxide such as perfluoroalkyltrimethylammonium salt, Perfluoroalkyl ethylene oxide adduct, oligomer containing perfluoroalkyl group and hydrophilic group, oligomer containing perfluoroalkyl group and lipophilic group, oligomer containing perfluoroalkyl group, hydrophilic group and lipophilic group, perfluoroalkyl group and parent Nonionic types such as oily group-containing urethanes may be mentioned.

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

Further, the developer and the developing replenisher may contain an organic solvent.

As the organic solvent, those having a solubility in water at 20 ° C. of 10% by weight or less are preferable. For example, ethyl acetate, propyl acetate, butyl acetate, benzyl acetate,
Ethylene glycol monobutyl acetate, butyl lactate,
Carboxylic acid esters such as butyl levulinate; ketones such as ethyl butyl ketone, methyl isobutyl ketone and cyclohexanone; ethylene glycol monobutyl ether, ethylene glycol benzyl ether, ethylene glycol monophenyl ether, benzyl alcohol, methylphenyl carbinol, n Alcohols such as amyl alcohol, methyl amyl alcohol;
Examples include alkyl-substituted aromatic hydrocarbons such as xylene; halogenated hydrocarbons such as methylene dichloride, ethylene dichloride, and monochlorobenzene.

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

Further, the following additives can be added to the developer and the development replenisher in order to enhance the developing performance. As these additives, for example, JP-A-58-75152
Neutral salts such as NaCl, KCl and KBr described in JP-A-59-190952, chelating agents such as EDTA and NTA described in JP-A-59-190952, and [Co (N) described in JP-A-59-121336.
H ₃ )] ₆ Cl _{3 and} other amphoteric polymer electrolytes such as copolymers of vinylbenzyltrimethylammonium chloride and sodium acrylate described in JP-A-56-142528, and JP-A-58-59444. Inorganic lithium compounds such as lithium chloride described, organolithium compounds such as lithium benzoate described in Japanese Patent Publication No. 50-34442, organometallic surfactants containing Si, Ti and the like described in JP-A-59-75255, An organic boron compound described in JP-A-59-84241 is exemplified.

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

[0102]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples.

Example 1 [Preparation of Aluminum Plate] An aluminum plate having a thickness of 0.3 mm (material: 1050, tempered H16) was subjected to a degreasing treatment in a 5% aqueous sodium hydroxide solution maintained at 65 ° C. for 1 minute. After that, it was washed with water, immersed in a 10% sulfuric acid aqueous solution kept at 25 ° C. for 1 minute,
Neutralized and washed with water. This aluminum plate was placed in a 1.0% by weight aqueous hydrochloric acid solution at a temperature of 25 ° C. and a current density of 100 A.
The electrolytic surface roughening was performed with an alternating current under the conditions of / dm ² and a processing time of 60 seconds. Then, in a 5% aqueous sodium hydroxide solution
Desmut treatment was performed at 60 ° C. for 10 seconds, and then anodization treatment was performed in a 20% sulfuric acid solution at a temperature of 20 ° C., a current density of 3 A / dm ² and a treatment time of 1 minute. Then, it was immersed in a 1% aqueous solution of sodium nitrite kept at 80 ° C. for 30 seconds, washed with water and dried at 80 ° C. for 3 minutes. Further, the substrate was immersed in an aqueous solution of carboxymethylcellulose (concentration: 0.1% by weight) kept at 85 ° C for 30 seconds, and dried at 80 ° C for 5 minutes to prepare a support.

[Preparation of photosensitive lithographic printing plate sample] The following photosensitive layer coating solution shown in Table 1 was applied to the above support using a wire bar, and dried under the following drying conditions shown in Table 1.
Photosensitive planographic printing plate samples 1 to 3 were prepared. The thickness of the photosensitive layer was 2.0 μm.

[0105]

[Table 1]

<Composition of photosensitive layer coating solution> (Photosensitive layer coating solution A) Novolak resin (phenol / m-cresol / p-cresol molar ratio is 10 / 54/36, weight average molecular weight 4000) 6.7g Pyrogallol acetone resin (weight average molecular weight 3000) and o-naphthoquinonediadi Condensation product of do-5-sulfonyl chloride (esterification rate 30%) 1.5 g Polyethylene glycol # 2000 0.2g Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) 0.08g 2,4-bis (trichloromethyl) -6- (p-methoxystyryl) -s-to Liazin 0.15g FC-430 (Sumitomo 3M Co., Ltd.) 0.03 g cis-1,2-cyclohexanedicarboxylic acid 0.2 g Methyl ethyl ketone / diethyl carbitol = 50/50                                                   100 ml

[0107] (Photosensitive layer coating solution B) Novolak resin (phenol / m-cresol / p-cresol molar ratio is 10 / 54/36, weight average molecular weight 4000) 6.7g Pyrogallol acetone resin (weight average molecular weight 3000) and o-naphthoquinonediadi Condensation product of do-5-sulfonyl chloride (esterification rate 30%) 0.2 g Polyethylene glycol # 2000 0.2g Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) 0.08g 2,4-bis (trichloromethyl) -6- (p-methoxystyryl) -s-to Liazin 0.15g FC-430 (Sumitomo 3M Co., Ltd.) 0.03 g cis-1,2-cyclohexanedicarboxylic acid 0.2 g Methyl ethyl ketone / diethyl carbitol = 50/50                                                   100 ml

[0108] (Photosensitive layer coating solution C) Novolak resin (phenol / m-cresol / p-cresol molar ratio is 10 / 54/36, weight average molecular weight 4000) 6.7g Pyrogallol acetone resin (weight average molecular weight 3000) and o-naphthoquinonediadi Condensation product of do-5-sulfonyl chloride (esterification rate 30%) 0.2 g Polyethylene glycol # 2000 0.2g Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) 0.08g 2,4-bis (trichloromethyl) -6- (p-methoxystyryl) -s-to Liazin 0.15g FC-430 (Sumitomo 3M Co., Ltd.) 0.03 g cis-1,2-cyclohexanedicarboxylic acid 0.2 g Methyl ethyl ketone / 2-methoxyethyl acetate = 4/1                                                   100 ml

[0109] (Photosensitive layer coating solution D) Novolak resin (phenol / m-cresol / p-cresol molar ratio is 10 / 54/36, weight average molecular weight 4000) 6.7g Pyrogallol acetone resin (weight average molecular weight 3000) and o-naphthoquinonediadi Condensation product of do-5-sulfonyl chloride (esterification rate 30%) 1.5 g Polyethylene glycol # 2000 0.2g Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) 0.08g 2,4-bis (trichloromethyl) -6- (p-methoxystyryl) -s-to Liazin 0.15g FC-430 (Sumitomo 3M Co., Ltd.) 0.03 g cis-1,2-cyclohexanedicarboxylic acid 0.2 g Methyl ethyl ketone / 2-methoxyethyl acetate = 4/1                                                   100 ml

<Drying conditions after application of photosensitive layer> (Drying condition A) Dry at 40 ° C for 1 minute (Drying condition B) Dry at 55 ° C for 1 minute (Drying condition C) Dry at 100 ° C for 1 minute

The sensitivity and printing durability of the obtained photosensitive lithographic printing plate samples were evaluated as follows. Table 2 shows the obtained results.

<< Evaluation Method >> = Evaluation of Sensitivity = A step tablet for sensitivity measurement (No. 2 manufactured by Eastman Kodak Co., Ltd., 21 levels of gray scale with a density difference of 0.15) was closely attached to the sample, and a 4 kW metal halide lamp (large) Exposure was performed from a distance of 90 cm using a Nippon Screen Co., Ltd. vio Quick) as a light source.

Next, this sample was developed at 27 ° C. for 20 seconds using a developer obtained by diluting an SDR-1 (manufactured by Konica Corporation) developer 6 times with water.

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

= Evaluation of printing durability = A 4 kW metal halide lamp (Dainippon Screen) with a step tablet for sensitivity measurement (No. 2 manufactured by Eastman Kodak Co., Ltd., 21 steps of gray scale with a density difference of 0.15) adhered to the sample. Exposure was performed from a distance of 90 cm using vio Quick (manufactured by Corporation) as a light source.

Next, this sample was developed at 27 ° C. for 20 seconds with a developer obtained by diluting an SDR-1 (manufactured by Konica Corporation) developer 6 times with water.

The obtained lithographic printing plate was applied to a printing machine GTO manufactured by Heidelberg Co., Ltd., and coated paper, printing ink (New Bright Red manufactured by Toyo Ink Mfg. Co., Ltd.) and dampening water (SEU-3 manufactured by Konica K.K.) ; 2.5%)
Printing was continued until an inking defect appeared on the solid portion of the image of the printed matter or ink was deposited on the non-image portion, and the number of printed sheets at that time was counted.

[0118]

[Table 2]

Further, the obtained photosensitive lithographic printing plate sample was
Atimo Bussan Co., Ltd. Grimm Glow Surface Analyzer JY5
Surface analysis was performed using OSS GDS, and Elem / Fi values of S atoms contained in the o-quinonediazide compound of the photosensitive layer and Al atoms contained in the support were measured as a function of time.
The obtained results are shown in FIGS. FIG. 1 shows sample 1
FIG. 2 shows the measurement result of Sample 3. 1 and 2, a large Elem / Fi value of the S atom indicates that the content of the o-quinonediazide compound on the surface at that time is large.

In FIGS. 1 and 2, Elem / Fi of S atom
When the value became equal to the Elem / Fi value of the Al atom, the photosensitive layer disappeared, and graininess of the support appeared.

As shown in FIG. 1, in Sample 1, the content of the condensate of pyrogallol acetone resin and o-naphthoquinonediazide-5-sulfonyl chloride in the photosensitive layer is the largest on the surface of the photosensitive layer.

[0122]

The photosensitive lithographic printing plate of the present invention has a wide range of suitable developing conditions, has sufficient printing durability without deterioration of film strength, and has sufficient sensitivity. .

[Brief description of the drawings]

[Fig. 1] Atago Bussan Co., Ltd.
It is a graph which shows the result of having performed the surface analysis using the grim glow surface analyzer JY50S GDS made by company.

[Fig. 2] Atago Bussan Co., Ltd.
It is a graph which shows the result of having performed the surface analysis using the grim glow surface analyzer JY50S GDS made by company.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-2-293750 (JP, A) JP-A-58-205154 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03F 7/00-7/18 G03F 7/26-7/42

Claims (1)

(57) [Claims] 1. A photosensitive lithographic printing plate comprising at least one photosensitive layer containing an o-quinonediazide compound and an alkali-soluble resin on a support, wherein the maximum concentration of the o-quinonediazide compound in the photosensitive layer is A method for producing a photosensitive lithographic printing plate, wherein the o-quinonediazide compound is contained in an amount of at least 5% by weight at room temperature , as viewed from the support side.
One solvent that can be dissolved , has a boiling point higher than that of the one solvent by 20 ° C. or more, and
Less than 5% by weight of o-quinonediazide compound
A coating solution obtained by dissolving a photosensitive composition containing an o-quinonediazide compound and an alkali-soluble resin in a mixed solvent with another solvent that is capable of acting on a support is applied to a support , and the temperature is low, high, and an intermediate temperature between the low and the high. Drying in the order of the low temperature, the intermediate temperature, and the high temperature under the three different temperature conditions.