JP2003098687A - Pre-burning counter-etching liquid and plate making method for planographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pre-burning counter-etching liquid which eliminates surface staining after a burning treatment and can impart a good lipid sensitization property and an excellent printing resistance improving effect to image areas and does not give rise to unevenness to the surface state after the burning, to provide a pre-burning counter-etching liquid which is suitable for automation by use of a processing machine of a spray circulation system or the like and to provide a plate making method capable of making a planographic printing plate which is free of defects in the image areas and exhibits excellent plate wear without the occurrence of staining in non-image areas. SOLUTION: The pre-burning counter-etching liquid containing soybean polysaccharides and the plate making method of subjecting the photosensitive planographic printing plate to exposure and development processing, then processing the plate with an aqueous solution containing the soybean polysaccharides then to a burning processing.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention uses a pre-burning surface-adjusting solution which is used after exposing and developing a photosensitive lithographic printing plate and before performing a burning treatment, and such a pre-burning surface-adjusting solution. The present invention relates to a method of making a planographic printing plate.

[0002]

2. Description of the Related Art Lithographic printing is a printing method that skillfully utilizes the property that water and oil are essentially immiscible, and the printing plate surface repels water and areas that repel oil-based ink and water. The former is a non-image area and the latter is an image area. For example, in a positive-working photosensitive lithographic printing plate, an o-quinonediazide compound is used alone or mixed with an alkali-soluble resin such as a novolac-type phenol resin or cresol resin, and coated on a suitable support such as metal or plastic. When exposed to actinic rays through a transparent positive image, the o-quinonediazide compound in the exposed portion decomposes and becomes alkali-soluble, and is easily removed by an aqueous alkali solution to give a positive image. Therefore, since the hydrophilic surface of the support is exposed at the portion removed by the aqueous alkaline solution using the support having the hydrophilic surface, this portion receives water and repels the ink. On the other hand, the portion remaining as an image is lipophilic and accepts ink.

When it is desired to obtain a large number of printed matter from one printing plate, after exposing and developing the photosensitive lithographic printing plate,
A method of strengthening the image portion by heating at a high temperature (so-called burning treatment) is effective. However, in the non-image area of the printing plate that was hydrophilic before the treatment (that is, the area where the hydrophilic support surface was exposed by development),
By performing the burning process, the components that fly out from the image portion become stains and lose their hydrophilicity, and the printing ink is received, so that stains (so-called background stains) occur on the background of the printed matter. Therefore, surface treatment is required to prevent the non-image area from being smeared by the burning process.

In the case of making an infrared-sensitive lithographic printing plate having an image-forming layer containing an infrared-absorbing dye, when the alkali concentration of the developer is increased to improve the developability of the non-image area, the image area of the image area is reduced. On the other hand, under the condition that the image portion is not thinned, the residual film is likely to remain in the non-image portion. Therefore, when the burning process is performed while adopting the developing condition in which the image portion is not thinned, the non-image portion is more likely to be soiled, and thus the burning treatment liquid becomes important especially in the plate making of the infrared-sensitive lithographic printing plate. come. Various proposals have hitherto been made as a surface-treating treatment liquid used before and / or after the burning treatment step.

As a treatment method for preventing the hydrophilicity of the non-image area from being lowered before the burning treatment, Japanese Patent Laid-Open No. 34001/1975 discloses that after alkali development,
It is described that the material is treated with an aqueous solution containing a sulfonate and further subjected to a burning treatment. When an aqueous solution of a sulfonate is used, it has a high foaming property and is unsuitable for use in a spray circulation type processing machine which is widely used at present, and there is a drawback that the plate making operation cannot be automated. Also,
Japanese Patent Publication No. 55-28062 discloses a method of treating with an aqueous solution containing sublimable boric acid and a salt thereof before the burning treatment, and performing the burning treatment in the presence of the compound. Was not adequately prevented.
In particular, water washing performed after the burning treatment, depending on the conditions such as gumming, that is, if the water washing is insufficient or the desensitizing gum solution is a dextrin type gum solution having a weak hydrophilicity, scumming occurs. There was a drawback that it was easy to happen.

Further, in JP-A-52-2205, a water-soluble organic substance such as gum arabic, cellulose ether, polyacrylic acid and / or borate, phosphate, sulfate, alkali metal or alkaline earth is used before the burning treatment. Although treatment with an aqueous solution of a water-soluble inorganic salt such as a halide of a group of metals has been shown, this method does not always completely prevent scumming, and especially gum arabic, polyacrylic acid, etc. When the aqueous solution of the water-soluble polymer is used, there is a drawback that it becomes difficult to receive the ink in the image portion at the time of printing, that is, a so-called inking defect occurs. Further, JP-A-57-52057 discloses a method of treating with an aqueous solution containing a carboxyl group-containing amine such as ethylenediaminetetraacetic acid or hydroxyalkylethylenediaminetriacetic acid or a salt thereof before the burning treatment. . However, this method also cannot be said to have a sufficient effect of preventing scumming.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is a pre-burning surface-adjusting liquid used for performing a burning treatment on an exposed / developed lithographic printing plate, which has no background stain after the burning treatment and has no image area. An object of the present invention is to provide a pre-burning surface-adjusting liquid capable of imparting excellent oil sensitivity and an excellent effect of improving printing durability. Another object of the present invention is to provide a surface conditioning liquid before burning which does not cause unevenness in the surface condition after burning. Another object of the present invention is to provide a pre-burning leveling solution suitable for automation by use of a spray circulation type processor or the like. It is a further object of the present invention to provide a plate-making method capable of producing a lithographic printing plate that has no defects in the image area, does not stain the non-image area, and exhibits excellent printing durability. is there.

[0008]

The present inventor uses an aqueous solution containing soybean polysaccharide as a treatment liquid (hereinafter referred to as a pre-burning surface-adjusting liquid) applied to a lithographic printing plate before the burning treatment. By doing so, they have found that the above objectives are achieved. Therefore, the present invention is a pre-burning surface conditioning solution characterized by containing soybean polysaccharide. The present invention is also directed to a pre-burning surface conditioning solution obtained by further adding a sulfonate to the aqueous solution containing the soybean polysaccharide. The present invention also relates to a method of making a lithographic printing plate, which comprises exposing a photosensitive lithographic printing plate to light, developing it, treating it with an aqueous solution containing soybean polysaccharide, and then performing a burning treatment. As a preferred embodiment of the plate-making method of the present invention, an infrared-sensitive lithographic printing plate having an image-forming layer containing an infrared absorber is exposed to infrared rays, subjected to development processing, and then treated with an aqueous solution containing soybean polysaccharide, and then, A plate-making method of performing a burning treatment can be mentioned.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The soybean polysaccharide used in the plate-making method of the present invention is a polysaccharide obtained by extracting raw soybean with water, which is a kind of polymer surfactant, mainly galactose,
It contains arabinose and galacturonic acid as constituents. The present inventor has found that the soaking polysaccharide-containing surface smoothing solution allows the soybean polysaccharide to spread evenly over the non-image area to form a film without fear of effervescence, resulting in good stains in the non-image area. I found that Commercially available soybean polysaccharides include Soyafive-S-LN and Soyafive-S-D.
N (both manufactured by Fuji Oil Co., Ltd.) and the like. The soybean polysaccharide that can be used in the present invention has an average molecular weight of 5 to 1,000,000 and a 10 mass% aqueous solution having a viscosity (25 ° C.) of 5 to 100 cp.
Those in the range of are preferably used. The pre-burning surface conditioning solution of the present invention is an aqueous solution containing such a soybean polysaccharide, and the content of the soybean polysaccharide in the aqueous solution is appropriately 0.01 to 45.0% by mass. , Preferably 0.1 to 30% by mass, more preferably 1.0 to 20
It is% by mass. If it is less than 0.01% by mass, there is no effect of removing the residual film in the non-image part, and if it exceeds 45.0% by mass, defects occur in the image part.

The surface-regulating liquid before burning of the present invention may further contain various additives. Examples of such additives include surfactants, various salts, acids and the like. The surfactant added helps the surface-regulating liquid before burning of the present invention to be uniformly applied to the surface of the lithographic printing plate, and also forms a coating on the non-image area to stain the non-image area due to the burning treatment. It also has a part of action to suppress the generation. Preferred surfactants are anionic surfactants, of which sulfonates are preferred. That is, the effect of improving the residual film on the non-image portion can be further improved by adding the sulfonate. The sulfonates include aromatic sulfonates and aliphatic sulfonates. As an aromatic sulfone salt, there is one represented by the following formula.

[0011]

[0012]

(In the above formulas [I] to [XIX], R represents a straight chain or branched alkyl group having 1 to 24 carbon atoms, and R ¹ is hydrogen or a straight chain having 1 to 24 carbon atoms. Or a branched alkyl group, R ² , R ³ , R ⁴ and R ⁵ each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 24 carbon atoms, M is an alkali metal, Represents ammonium or amine, n is 0 or 1, n'is 0 or 1, and m is 1.
Or 2, p is 0, 1 or 2, q is 0, 1 or 2,
However, p + q is 1 or more, and X is -O-, -S-,-.
CO -, - NH -, - SO -, - SO 2 -, - CH 2 -,
-CH (OH) -, or _{- (CH 3) C (CH} 3) - represents a. ) Among the above-mentioned alkali metals, sodium, potassium and lithium can be mentioned. Specific examples of the above compounds include sodium dodecylphenoxybenzenedisulfonate, sodium alkylnaphthalenesulfonate, sodium methylenedinaphthalenesulfonate, sodium dodecylbenzenesulfonate and the like.

Aliphatic sulfonates are generally R--SO ₃
M (wherein R represents a saturated hydrocarbon group or an unsaturated hydrocarbon group having 1 to 24 carbon atoms, and M represents an alkali metal, ammonium or amine).
The hydrocarbon group may be linear or branched, may be substituted with a halogen atom or an ester group, and
When the methylene group in the hydrocarbon group is -C (O) N (R ')-
(In the formula, R ′ represents an alkyl group or a hydrogen atom). Examples of the alkali metal include sodium, potassium and lithium. Specific compounds include sodium dioctylsulfosuccinate, sodium dimethylamylsulfosuccinate, sodium dialkylsulfosuccinate, ammonium or potassium perfluoroalkylsulfonate, sodium α-olefinsulfonate, and the like.

The concentration of the sulfonate in the aqueous solution is suitably 0.01 to 45.0% by mass, preferably 0.1 to 30% by mass, more preferably 1.0 to
It is 20% by mass. If it is less than 0.01% by mass, there is no effect of removing the residual film in the non-image part, and if it exceeds 45.0% by mass, defects occur in the image part. In the above aqueous solution used in the method of the present invention, an acid such as citric acid,
And a base such as sodium hydroxide or potassium hydroxide
It may be added to adjust H. The concentration is generally 0.01 to 10 mass% in the total amount of the aqueous solution. The surface conditioning solution before burning is generally used in a pH range of 2 to 12, preferably 2.5 to 10. With the pH in such a range, not only the surface conditioning solution before burning can be safely handled, but also the etching action on the aluminum support can be suppressed, and the hydrophilicity of the aluminum oxide surface of the support is deteriorated. Can be prevented.

The pre-burning surface-adjusting solution of the present invention can be applied to the plate making of various photosensitive lithographic printing plates, and includes positive / negative photosensitive lithographic printing plates, photopolymerizable photosensitive lithographic printing plates, and negative lithographic printing plates. It can be used for any processing of positive-working and positive working infrared-sensitive lithographic printing plates. Further, the exposure process and the development process can be carried out according to a conventional method. In recent years, automatic developing machines for printing plate materials have been widely used in the plate making / printing industry for streamlining and standardizing plate making work. This automatic developing machine is generally composed of a developing section and a post-processing section, and is composed of a device for conveying a printing plate material, each processing liquid tank, and a spray device. Each of the processing liquids pumped up is sprayed from a spray nozzle for development processing. Further, recently, a method has also been known in which a printing plate material is immersed and conveyed by a submerged guide roll or the like in a treatment liquid tank filled with the treatment liquid to perform treatment. In such automatic processing, it is possible to perform processing while replenishing each processing solution with a replenishing solution according to the processing amount, operating time, and the like. In addition, treatment with each treatment liquid that is substantially unused,
A so-called disposable processing method can also be used.

The application of the surface conditioning solution before burning of the present invention can be carried out by the general automatic developing machine as described above. The pre-burning surface-adjusting solution of the present invention is applied to the photosensitive lithographic printing plate after imagewise exposure, development and, if necessary, washing with water, and before the burning treatment. The surface conditioning solution before burning has a liquid temperature of 15
Suitably used at ~ 35 ° C. How to use
As with the gum solution, it is suitable to spray and homogenize on a roll. The lithographic printing plate coated with the surface conditioning solution before burning is dried if necessary and then heated to a high temperature with a burning processor (for example, Burning Processor 1300 sold by Fuji Photo Film Co., Ltd.). The heating temperature and time in this case are 180 to 300, depending on the type of components forming the image.
The temperature is preferably in the range of 1 to 20 minutes. The planographic printing plate that has been subjected to the burning treatment can be directly subjected to the printing process. Alternatively, if necessary, a conventional treatment such as washing with water or gumming with a desensitizing solution containing gum arabic or a starch derivative can be performed.

The plate-making method using the pre-burning surface-adjusting solution of the present invention is particularly preferably applied to plate-making using an infrared-sensitive lithographic printing plate having an image forming layer containing an infrared absorber. Hereinafter, a general infrared-sensitive lithographic printing plate to which the plate making method of the present invention can be applied, and a general alkali developing solution used in the plate making method of the present invention will be described. The infrared-sensitive lithographic printing plate comprises an image-forming layer on a support and, if necessary, other layers. The image-forming layer comprises (A) an infrared absorber and (B) an alkali-soluble layer. A compound containing a polymer compound, which is further compatibilized with (C) an alkali-soluble polymer compound to reduce the solubility of the alkali-soluble polymer compound in an alkaline aqueous solution, and to reduce the solubility-reducing action by heating. ,
(D) Cyclic acid anhydride and the like may be contained. In the case of a negative type lithographic printing plate precursor, the exposed area is cured to form an image area. Therefore, the compound (A) which generates an acid by heat is crosslinked with the acid (F) in the image forming layer. And a cross-linking agent. Hereinafter, each component will be briefly described.

-(A) Infrared absorbing agent-The infrared absorbing agent (hereinafter sometimes referred to as "(A)" component ") has a function of converting absorbed infrared rays into heat. As the usable infrared absorbing agent, a dye or pigment capable of absorbing infrared rays in a wavelength range of 700 nm or more, preferably in a wavelength range of 750 nm to 1200 nm with high efficiency is preferable, and an absorption maximum in a wavelength range of 760 nm to 1200 nm. More preferred are dyes or pigments having.

Examples of the dye material include commercially available dyes and known dyes described in the literature (for example, "Handbook of Dyes", edited by The Society of Synthetic Organic Chemistry, published in 1945). For example, azo dyes and metal complex salts azo. Examples thereof include dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinonimine dyes, methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, and metal thiolate complexes.

Among them, for example, JP-A-58-12524
6, JP-A-59-84356, JP-A-59-202.
829, cyanine dyes described in JP-A-60-78787, JP-A-58-173696, JP-A-58-1.
81690, methine dyes described in JP-A-58-194595, JP-A-58-112793, and JP-A-58.
-224793, JP-A-59-48187, JP-A-59-73996, JP-A-60-52940, JP-A-60-63744, and the like, naphthoquinone dyes, JP-A-58-112792, and the like. Preferable examples thereof include the squarylium dye described in JP-A No. 434,875, the cyanine dye described in British Patent 434,875, and the dihydroperimidine squarylium dye described in US Pat. No. 5,380,635.

The near-infrared absorption sensitizers described in US Pat. No. 5,156,938 are also preferable, and the substituted arylbenzo (thio groups described in US Pat. No. 3,881,924 are also preferable. ) Pyrylium salt, JP-A-57-1426
45 (US Pat. No. 4,327,169), a trimethine thiapyrylium salt, JP-A-58-1810.
No. 51, No. 58-220143, No. 59-41363.
No. 59-84248, No. 59-84249, No. 59-146063, No. 59-146061, cyanine dyes described in JP-A No. 59-216146, U.S. Pat. No. 283,475, pentamethine thiopyrium salt, etc., Japanese Patent Publication Nos. 5-13514 and 5-19702, pyrilium compounds, and commercially available products, Epolight III-178, E
polight III-130, Epolight III-125, Epolight
IV-62A (manufactured by Eporin) and the like are also preferable.

Further, near-infrared absorbing dyes represented by the formulas (I) and (II) described in US Pat. No. 4,756,993 can also be mentioned as preferable ones. Among the above, a cyanine dye, a squarylium dye, a pyrylium salt, and a nickel thiolate complex are more preferable.

As the above-mentioned pigments, commercially available pigments or color index (CI) handbook, "Latest pigment handbook" (edited by Japan Pigment Technology Association), 1977), "Latest pigment application technology" (CMC Publishing, 1986) Annually), "Printing Ink Technology" (CMC Publishing, 1984), and examples thereof include black pigments, yellow pigments, orange pigments, brown pigments, red pigments, purple pigments, blue pigments, green pigments, Fluorescent pigments, metal powder pigments, and other polymer-bonded dyes are mentioned.

Specifically, for example, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelate azo pigments, phthalocinanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, Isoindolinone pigment, quinophthalone pigment, dyed lake pigment, azine pigment, nitroso pigment, nitro pigment, natural pigment, fluorescent pigment,
Examples include inorganic pigments and carbon black. Above all,
Carbon black is preferred.

The pigment may be used without surface treatment, or may be used after surface treatment. As a method of surface treatment, a method of surface coating resin or wax,
Examples thereof include a method of attaching a surfactant and a method of binding a reactive substance (for example, a silane coupling agent, an epoxy compound, polyisocyanate, etc.) to the pigment surface.
The method of these surface treatments is "property and application of metallic soap".
(Koshobo), "Printing ink technology" (CMC Publishing, 198)
4 years) and "Latest pigment application technology" (CMC Publishing, 19
1986).

The particle size of the pigment is 0.01 μm to 1
0 μm is preferable, 0.05 μm to 1 μm is more preferable, and 0.1 μm to 1 μm is most preferable. The particle size is 0.
If it is less than 01 μm, the stability of the dispersion when the dispersion such as the photosensitive layer coating solution is prepared may deteriorate.
When it exceeds μm, the uniformity of the image forming layer may deteriorate.

The method for dispersing the pigment can be appropriately selected from known dispersing techniques such as a general-purpose disperser for ink production and toner production. Examples of the disperser include an ultrasonic disperser, a sand mill, an attritor, a pearl mill, a super mill, a ball mill, an impeller, a desperzer,
A KD mill, a colloid mill, a dynatron, a three roll mill, a pressure kneader and the like can be mentioned. The details are described in "Latest Pigment Application Technology" (CMC Publishing, 1986).

The content of the dye or pigment is preferably 0.01 to 50% by mass, more preferably 0.1 to 10% by mass, and more preferably 0.1 to 10% by mass based on the total mass of the solid content of the image forming layer. Is most preferably 0.5 to 10% by mass, and in the case of a pigment, 3.1 to 10% by mass is most preferable. If the content is less than 0.01% by mass, the sensitivity may be lowered, and if it exceeds 50% by mass, the uniformity of the image forming layer may be deteriorated and the durability thereof may be deteriorated.

The dye or pigment may be added to the same layer as other components, or may be added to another layer provided separately. When it is formed as another layer, it is preferably added to a layer adjacent to the layer containing the component (C) described later. Further, the dye or pigment and the alkali-soluble polymer compound are preferably contained in the same layer, but may be contained in different layers.

-(B) Alkali-soluble polymer compound-A usable alkali-soluble polymer compound (hereinafter,
Sometimes referred to as "(B) component". As the above), an alkaline water-soluble polymer compound having the following acidic groups (1) to (3) in the main chain and / or side chain structure can be used. (1) phenol group (-Ar-OH) (2) sulfonamide group _{(-SO 2 NH-R) (} 3) substituted sulfonamide-based acid group (hereinafter, referred to as "active imide group".) [-SO ₂ NHCOR , -SO ₂ NHSO ₂ R, -CON
HSO ₂ R] In the above (1) to (3), Ar represents a divalent aryl linking group which may have a substituent, and R represents a hydrocarbon group which may have a substituent. Represent Specific examples thereof are shown below, but the present invention is not limited thereto.

(1) Examples of the alkali-soluble polymer compound having a phenol group include a condensation polymer of phenol and formaldehyde, a condensation polymer of m-cresol and formaldehyde, and a condensation polymer of p-cresol and formaldehyde. , A condensation polymer of m- / p-mixed cresol and formaldehyde, phenol and cresol (m
Any of-, p- or m- / p- mixture may be used. A novolak resin such as a condensation polymer of) and formaldehyde, or a condensation polymer of pyrogallol and acetone. Further, a polymer compound obtained by polymerizing a monomer having a phenol group in its side chain can also be mentioned.

As the polymer compound having a phenolic hydroxyl group in the side chain, a polymerizable monomer composed of a low molecular weight compound each having one or more unsaturated bonds capable of polymerizing with the phenolic hydroxyl group is homopolymerized, or the polymerizable compound Examples thereof include polymer compounds obtained by copolymerizing a monomer with another polymerizable monomer. Examples of the monomer having a phenol group in its side chain include acrylamide, methacrylamide, acrylic acid ester, methacrylic acid ester, hydroxystyrene and the like having a phenol group in its side chain.

Specifically, N- (2-hydroxyphenyl) acrylamide, N- (3-hydroxyphenyl)
Acrylamide, N- (4-hydroxyphenyl) acrylamide, N- (2-hydroxyphenyl) methacrylamide, N- (3-hydroxyphenyl) methacrylamide, N- (4-hydroxyphenyl) methacrylamide, o-hydroxyphenyl acrylate , M-hydroxyphenyl acrylate, p-hydroxyphenyl acrylate, o-hydroxyphenyl methacrylate, m-hydroxyphenyl methacrylate, p-hydroxyphenyl methacrylate, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, 2- (2 -Hydroxyphenyl) ethyl acrylate, 2- (3-hydroxyphenyl) ethyl acrylate, 2- (4-hydroxyphenyl) ethyl acrylate, 2- (2-hydro) Shifeniru) ethyl methacrylate, 2- (3-hydroxyphenyl) ethyl methacrylate, 2- (4-hydroxyphenyl) ethyl methacrylate can be preferably exemplified.

Alkali-soluble having the above-mentioned phenol group
The weight average molecular weight of the polymer compound is 5.0 × 10.²
~ 2.0 x 10^FiveHas a number average molecular weight of 2.0.
× 10 ²~ 1.0 x 10^FiveAre preferable in terms of image forming property.
Good In addition, the alkali-soluble high content of phenol group
Sub-compounds can be used alone or in combination of two or more.
You may use together. If you want to combine,
As described in U.S. Pat. No. 4,123,279,
Condensation polymer of t-butylphenol and formaldehyde
And polycondensation of octylphenol and formaldehyde
Body-like alkyl group having 3 to 8 carbon atoms as a substituent
The condensation polymer of phenol and formaldehyde
May be used. These polycondensates also have a weight average molecular weight of
5.0 x 10²~ 2.0 x 10^FiveHaving a number average molecular weight of 2.0
× 10²~ 1.0 x 10^FiveAre preferred.

(2) Examples of the alkali-soluble polymer compound having a sulfonamide group include, for example, a polymer having a compound having a sulfonamide group as a main monomer constituent unit, that is, a homopolymer or another monomer constituent unit. Examples thereof include a copolymer obtained by copolymerizing a polymerizable monomer. Examples of the polymerizable monomer having a sulfonamide group include a sulfonamide group —SO ₂ —NH— having at least one hydrogen atom bonded to a nitrogen atom in one molecule,
Examples of the monomer include a low molecular weight compound having one or more polymerizable unsaturated bonds. Among them, a low molecular weight compound having an acryloyl group, an allyl group or a vinyloxy group and a substituted or mono-substituted aminosulfonyl group or a substituted sulfonylimino group is preferable. Examples of the low molecular weight compounds include compounds represented by the following general formulas (a) to (e), but the present invention is not limited thereto.

[0037]

In the formula, X ¹ and X ² each independently represent an oxygen atom or NR ⁷ . R ¹ and R ⁴ each independently represent a hydrogen atom or CH ₃ . R ² , R ⁵ , R ⁹ , R ¹² , and R ¹⁶ are
Each independently has 1 to 1 carbon atoms which may have a substituent.
2 represents an alkylene group, a cycloalkylene group, an arylene group or an aralkylene group. R ³ , R ⁷ , and R ¹³ each independently represent a hydrogen atom or a carbon atom which may have a substituent.
~ 12 represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. R ⁶ and R ¹⁷ each independently represent an alkyl group having 1 to 12 carbon atoms, which may have a substituent, a cycloalkyl group, an aryl group or an aralkyl group. R ⁸ , R ¹⁰ and R ¹⁴ each independently represent a hydrogen atom or CH ₃ . R ¹¹ and R ¹⁵ each independently represent a single bond or an alkylene group having 1 to 12 carbon atoms which may have a substituent, a cycloalkylene group, an arylene group or an aralkylene group. Y ¹ and Y ² each independently represent a single bond or CO.

Among them, m-aminosulfonylphenyl methacrylate, N- (p-aminosulfonylphenyl) methacrylamide, N- (p-aminosulfonylphenyl) acrylamide and the like can be preferably used.

(3) Examples of the alkali-soluble polymer compound having an active imide group include polymers having a compound having an active imide group as a main monomer constituent unit. As a polymer having a compound having an active imide group as a main monomer constitutional unit,
Obtained by homopolymerizing a monomer composed of a low molecular weight compound having an active imide group represented by the following formula and at least one polymerizable unsaturated bond, or by copolymerizing the monomer with another polymerizable monomer. A high molecular compound can be mentioned.

[0041]

Specific examples of such a compound include:
N- (p-toluenesulfonyl) methacrylamide, N
Preferable examples thereof include-(p-toluenesulfonyl) acrylamide. Further, in addition to the above, a polymer compound obtained by polymerizing any two or more of the above-mentioned polymerizable monomer having a phenol group, a polymerizable monomer having a sulfonamide group, and a polymerizable monomer having an active imide group, or Further, a polymer compound obtained by copolymerizing these two or more kinds of polymerizable monomers with another polymerizable monomer is also preferable.

A polymerizable monomer having a phenol group (M
1), a polymerizable monomer having a sulfonamide group (M
The compounding ratio (M1: M2 and / or M3; mass ratio) when 2) and / or the polymerizable monomer (M3) having an active imide group is copolymerized is 50:50 to 5:95.
Is preferred, and 40:60 to 10:90 is more preferred.

The alkali-soluble polymer compound is a copolymer composed of a monomer constitutional unit having any one of the acidic groups (1) to (3) and a constitutional unit of another polymerizable monomer. In this case, it is preferable that the copolymer contains 10 mol% or more of a monomer structural unit having any one selected from the acidic groups (1) to (3).
It is more preferable to contain 0 mol% or more. If the content of the monomer structural unit is less than 10 mol%, sufficient alkali solubility may not be obtained and the development latitude may be narrowed. As a method for synthesizing the copolymer, a conventionally known graft copolymerization method, block copolymerization method, random copolymerization method or the like can be used.

A monomer having any one of the acidic groups (1) to (3) is copolymerized with a polymerizable monomer having a constituent unit. Examples of the other polymerizable monomer include the monomers listed in (a) to (1) below, but the present invention is not limited thereto.

(A) Acrylic acid esters and methacrylic acid esters having an aliphatic hydroxyl group such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate. (B) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, benzyl acrylate, 2-chloroethyl acrylate, glycidyl acrylate, N-dimethylaminoethyl Alkyl acrylate such as acrylate. (C) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 2-chloroethyl methacrylate, glycidyl methacrylate, N-dimethylaminoethyl. Alkyl methacrylate such as methacrylate.

(D) Acrylamide, methacrylamide, N-methylolacrylamide, N-ethylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide , Acrylamide such as N-ethyl-N-phenylacrylamide, or methacrylamide. (E) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether and phenyl vinyl ether. (F) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate. (G) Styrene, α-methylstyrene, methylstyrene, chloromethylstyrene and the like and styrenes.

(H) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone and phenyl vinyl ketone. (I) Olefins such as ethylene, propylene, isobutylene, butadiene and isoprene. (J) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, acrylonitrile, methacrylonitrile and the like. (K) maleimide, N-acryloyl acrylamide,
Unsaturated imides such as N-acetylmethacrylamide, N-propionylmethacrylamide, and N- (p-chlorobenzoyl) methacrylamide. (L) Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride, and itaconic acid.

The alkali water-soluble polymer compound, regardless of homopolymer or copolymer, is
Weight average molecular weight of 2000 or more, number average molecular weight of 500
The above is preferable, and the weight average molecular weight is 5,000 to 3
00000, the number average molecular weight is 800 to 250,000, and the dispersity (weight average molecular weight / number average molecular weight) is 1.1 to
10 is more preferable. Further, the alkali-soluble polymer compound, phenol-formaldehyde resin,
In the case of a cresol-aldehyde resin or the like, those having a weight average molecular weight of 500 to 20,000 and a number average molecular weight of 200 to 10,000 are preferable.

The content of the alkaline water-soluble polymer compound is 30 to 30 with respect to the total solid content of the image forming layer.
99 mass% is preferable, 40-95 mass% is more preferable, 50-90 mass% is the most preferable. The content is
If it is less than 30% by mass, the durability of the image forming layer may decrease, and if it exceeds 99% by mass, the sensitivity and durability may decrease. Further, the polymer compound may be used alone or in combination of two or more kinds.

-(C) A compound which is compatible with the alkali-soluble polymer compound to reduce the solubility of the alkali-soluble polymer compound in an aqueous alkali solution, and which reduces the solubility-reducing action by heating- The component (C) has good compatibility with the above-mentioned (B) alkali-soluble polymer compound due to the function of the hydrogen-bonding functional group present in the molecule, and can form a uniform coating liquid for the image-forming layer. At the same time, it refers to a compound having a function of suppressing the alkali solubility of the alkali-soluble polymer compound by the interaction with the alkali-soluble polymer compound (solubility suppressing action).

Although the above-described solubility-suppressing action on the alkali-soluble polymer compound disappears by heating, when the infrared absorbent itself is a compound that decomposes by heating, sufficient energy for decomposition is obtained by laser output or laser output. If it is not given under various conditions such as irradiation time, the solubility-suppressing action of the alkali-soluble polymer compound cannot be sufficiently lowered, and the sensitivity may be lowered. For this reason,
The thermal decomposition temperature of the component (C) is preferably 150 ° C or higher.

As the component (C), in consideration of the interaction with the alkali-soluble polymer compound (B), for example,
It can be appropriately selected from compounds capable of interacting with the alkali-soluble polymer compound, such as sulfone compounds, ammonium salts, phosphonium salts, and amide compounds.
In particular, for example, when a novolac resin is used alone as the component (B), the “(A + C) component” described below is used.
Is preferred, and the cyanine dye A exemplified below is more preferred. The component (A + C) will be described later. Generally, the compounding ratio (C / B) of the component (C) and the alkali-soluble polymer compound (B) is preferably 1/99 to 25/75. When the mixing ratio is less than 1/99, that is, when the amount of the component (C) is too small, the interaction with the alkali-soluble polymer compound becomes insufficient, the alkali solubility cannot be lowered, and good image formation is achieved. If it exceeds 25/75, that is, if the amount of component (C) is too large, the interaction may become excessive and the sensitivity may be significantly reduced.

-(A + C) component-In place of the (A) component and the (C) component, a compound ((A + C) component) having both properties can be used. The component (A + C) has a property of absorbing light to generate heat (that is, the property of the component (A)), and
It is a basic dye that has an absorption region in the wavelength region of 0 to 1200 nm and is also compatible with alkali-soluble polymer compounds. The component (A + C) has a group that interacts with the alkali-soluble polymer compound such as an ammonium group and an iminium group in its molecule (that is, the characteristic of the component (C)), and therefore it interacts with the polymer compound. , Its alkali solubility can be suppressed. Examples of the component (A + C) include compounds represented by the following general formula (Z).

[0055]

In the general formula (Z), R ^{21 to} R ²⁴ are each independently a hydrogen atom or an optionally substituted alkyl group having 1 to 12 carbon atoms, an alkenyl group, an alkoxy group, cyclo It represents an alkyl group or an aryl group, and R ²¹ and R ²² , and R ²³ and R ²⁴ may be bonded to each other to form a ring structure. Examples of R ^{21 to} R ²⁴ include a hydrogen atom,
Examples thereof include a methyl group, an ethyl group, a phenyl group, a dodecyl group, a naphthyl group, a vinyl group, an allyl group and a cyclohexyl group, and these groups may further have a substituent. Here, as the substituent, for example, a halogen atom,
Carbonyl group, nitro group, nitrile group, sulfonyl group,
Examples thereof include a carboxyl group, a carboxylic acid ester, and a sulfonic acid ester.

In the formula, R ^{25 to} R ³⁰ each independently represent an alkyl group having 1 to 12 carbon atoms which may have a substituent, and examples of R ^{25 to} R ³⁰ include a methyl group, Examples thereof include an ethyl group, a phenyl group, a dodecyl group, a naphthyl group, a vinyl group, an allyl group and a cyclohexyl group, and these groups may further have a substituent. Here, as the substituent, for example, a halogen atom, a carbonyl group,
Examples thereof include nitro group, nitrile group, sulfonyl group, carboxyl group, carboxylic acid ester and sulfonic acid ester.

In the formula, R ^{31 to} R ³³ each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms which may have a substituent, and R ³² is the above R ^31. Alternatively, it may combine with R ³³ to form a ring structure, and when m> 2, a plurality of R ^{32 s} may combine with each other to form a ring structure. Examples of R ^{31 to} R ³³ include a chlorine atom, a cyclohexyl group, a cyclopentyl ring formed by combining R ^32's , a cyclohexyl ring, and the like, and these groups may further have a substituent. .. Here, as the substituent, for example, a halogen atom, a carbonyl group, a nitro group, a nitrile group, a sulfonyl group, a carboxyl group,
Examples thereof include carboxylic acid ester and sulfonic acid ester. Moreover, m represents the integer of 1-8, and 1-3 are preferable especially.

In the formula, R ^{34 to} R ³⁵ each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms which may have a substituent, and R ³⁴ is the same as R ³⁵ . They may be bonded to each other to form a ring structure, and when m> 2, a plurality of R ³⁴ 's may be bonded to each other to form a ring structure. Examples of R ^{34 to} R ³⁵ include a chlorine atom, a cyclohexyl group, a cyclopentyl ring formed by combining R ^34's , a cyclohexyl ring, and the like, and these groups may further have a substituent. .. Here, examples of the substituent include a halogen atom, a carbonyl group, a nitro group, a nitrile group, a sulfonyl group, a carboxyl group, a carboxylic acid ester, a sulfonic acid ester, and the like. Also, m
Represents an integer of 1 to 8, and among them, 1 to 3 are preferable.

In the formula, X ⁻ represents an anion, for example,
Perchloric acid, tetrafluoroboric acid, hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid, 5-nitro-O-toluenesulfonic acid, 5-sulfosalicylic acid, 2,5-dimethylbenzenesulfonic acid, 2,4. 6-trimethylbenzenesulfonic acid, 2-nitrobenzenesulfonic acid, 3-
Chlorobenzenesulfonic acid, 3-bromobenzenesulfonic acid, 2-fluorocaprylnaphthalenesulfonic acid, dodecylbenzenesulfonic acid, 1-naphthol-5-sulfonic acid, 2-methoxy-4-hydroxy-5-benzoyl-benzenesulfonic acid and para. Examples include toluene sulfonic acid. Of these, alkylaromatic sulfonic acids such as hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid, and 2,5-dimethylbenzenesulfonic acid are preferable.

The compound represented by the general formula (Z) is a compound generally called a cyanine dye, and specifically, the compounds shown below are preferably used, but in the present invention, the compounds are not limited thereto. Not a thing.

When the component (A + C) having both characteristics is used in place of the component (A) and the component (C), the ratio of the amount of the component (A + C) and the component (B) used []. As (A + C) / (B)], 1/99 to 30
/ 70 is preferable, and 1/99 to 25/75 is more preferable.

-(D) Cyclic acid anhydride-A cyclic acid anhydride may be further used in the lithographic printing plate precursor. The cyclic acid anhydride has a bond conjugated to the carbonyl group of the carboxylic acid anhydride in its structure, the decomposition rate is controlled by increasing the stability of the carbonyl group, and the cyclic acid anhydride decomposes at an appropriate rate during storage. And generate acid. Therefore, it is possible to suppress the deterioration of the developability over time and to maintain the developability stably for a long period of time. Examples of the cyclic acid anhydride include compounds represented by the following general formula (I) or (II).

[0064]

In the general formula (I), R ⁴¹ and R ⁴² are each independently a hydrogen atom or an optionally substituted alkyl group having 1 to 12 carbon atoms, an alkenyl group, an alkoxy group or a cycloalkyl group. Represents a group, an aryl group, a carbonyl group, a carboxy group or a carboxylic acid ester. In addition,
R ⁴¹ and R ⁴² may combine with each other to form a ring structure.
Preferable examples of R ⁴¹ and R ⁴² include a hydrogen atom, or an unsubstituted alkyl group having 1 to 12 carbon atoms, an aryl group, an alkenyl group, a cycloalkyl group, and the like. Methyl group, ethyl group, phenyl group,
Examples thereof include a dodecyl group, a naphthyl group, a vinyl group, an allyl group, a cyclohexyl group, and these groups may further have a substituent. When R ⁴¹ and R ⁴² are linked to each other to form a ring structure, examples of the cyclic group include a phenylene group, a naphthylene group, a cyclohexene group and a cyclopentene group. Examples of the substituent include a halogen atom, a hydroxy group, a carbonyl group, a sulfonic acid ester, a nitro group and a nitrile group.

In the general formula (II), R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶
Are each independently a hydrogen atom, a hydroxyl group, a halogen atom such as chlorine, a nitro group, a nitrile group, or an optionally substituted alkyl group having 1 to 12 carbon atoms, an alkenyl group, an alkoxy group, a cyclo group. It represents an alkyl group, an aryl group, a carbonyl group, a carboxy group, a carboxylic acid ester group, or the like. Examples of R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ include a hydrogen atom, a halogen atom and a carbon atom of 1
Preferable examples thereof include an unsubstituted alkyl group having ˜12, an alkenyl group and an aryl group having 6 to 12 carbon atoms, and specific examples thereof include a methyl group, a vinyl group, a phenyl group and an allyl group. These groups may further have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, a carbonyl group, a sulfonic acid ester, a nitro group, a nitrile group and a carboxy group.

As the cyclic acid anhydride, for example, phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, 3-hydroxyphthalic anhydride,
3-methylphthalic anhydride, 3-phenylphthalic anhydride,
Preferable examples include trimellitic anhydride, pyromellitic anhydride, maleic anhydride, phenylmaleic anhydride, dimethylmaleic anhydride, dichloromaleic anhydride and chloromaleic anhydride. The content of the cyclic acid anhydride is preferably 0.5 to 20% by mass, more preferably 1 to 15% by mass, and 1 to 1 with respect to the total solid content of the image forming layer.
Most preferred is 0% by weight. When the content is less than 0.5% by mass, the effect of maintaining developability may be insufficient,
If it exceeds 20% by mass, an image may not be formed.

The following are components constituting the recording layer of the negative type lithographic printing plate. — (E) Compound that Generates Acid by Heat— When the image forming material is a negative type, a compound that generates an acid when heated (hereinafter, referred to as “acid generator”) is used in combination. This acid generator decomposes when heated to 100 ° C. or higher to increase the compound that generates an acid. As the acid generated,
A strong acid having a pKa of 2 or less, such as sulfonic acid or hydrochloric acid, is preferable. The acid generator, iodonium salt,
Preferable examples are onium salts such as sulfonium salts, phosphonium salts and diazonium salts. In particular,
U.S. Pat. No. 4,708,925 and JP-A-7-20629
The compounds described in JP-A No. 2004-242242 can be mentioned, and among them, iodonium salts, sulfonium salts, and diazonium salts having a sulfonate ion as a counter ion are preferable.

Examples of the diazonium salt include diazonium salt compounds described in US Pat. No. 3,867,147,
Diazonium compounds described in U.S. Pat. No. 2,632,703, JP-A-1-102456 and JP-A-1-
The diazo resin described in each publication of 102457 can also be mentioned suitably. Also, US Pat. No. 5,135,83
No. 8, benzyl sulfonates described in US Pat. No. 5,200,544, active sulfonic acid esters and disulfonyls described in JP-A Nos. 2-100054, 2-100055, and 8-9444. Compounds are also preferred. In addition, haloalkyl-substituted S-triazines described in JP-A-7-271029 are also preferable. The amount of the acid generator added is preferably 0.01 to 50% by mass, and 0.1 to 40% by mass based on the total solid content of the image forming layer.
Is more preferable, and 0.5 to 30 mass% is the most preferable.

-(F) Acid-crosslinking agent-When the lithographic printing plate precursor is a negative type, an acid-crosslinking agent (hereinafter sometimes simply referred to as "crosslinking agent") is used in combination. The following can be mentioned as said crosslinking agent. (I) Aromatic compound substituted with alkoxymethyl group or hydroxymethyl group (ii) Compound having N-hydroxymethyl group, N-alkoxymethyl group or N-acyloxymethyl group (iii) Epoxy compound Examples thereof include those described in JP-A-254850 and phenol derivatives.

The amount of the cross-linking agent added is preferably 5 to 80 mass% with respect to the total solid mass of the image forming layer.
-75 mass% is more preferable, and 20-70 mass% is the most preferable. When the phenol derivative is used as a crosslinking agent, the amount of the phenol derivative added is preferably 5 to 70% by mass, and more preferably 10 to 50% by mass, based on the total solid mass of the image forming material. Details of the above various compounds are described in JP-A-2000-267265.

-Other Components-Various additives may be further added to the image forming layer of the lithographic printing plate precursor, if necessary. For example, known additives such as phenols, organic acids and sulfonyl compounds can be used in combination for the purpose of improving sensitivity. Examples of phenols include bisphenol A, p-nitrophenol, p-ethoxyphenol, 2,4.
4'-trihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 4-hydroxybenzophenone, 4,4 ', 4 "-trihydroxytriphenylmethane, 4,4', 3", 4 "-tetrahydroxy-
3,5,3 ', 5'-tetramethyltriphenylmethane and the like can be mentioned.

Examples of the organic acids include those disclosed in JP-A-60-8.
There are sulfonic acids, sulfinic acids, alkylsulfuric acids, phosphonic acids, phosphoric acid esters, carboxylic acids and the like described in Japanese Patent Publication No. 8942, Japanese Patent Application Laid-Open No. 2-96755 and the like, and specifically, p-toluene. Sulfonic acid, dodecylbenzenesulfonic acid, p-toluenesulfinic acid, ethylsulfate, phenylphosphonic acid, phenylphosphinic acid, phenyl phosphate, diphenyl phosphate, benzoic acid, isophthalic acid, adipic acid, p-toluic acid,
Examples thereof include 3,4-dimethoxybenzoic acid, phthalic acid, terephthalic acid, 4-cyclohexene-2,2-dicarboxylic acid, erucic acid, lauric acid, n-undecanoic acid, and ascorbic acid. Examples of the sulfonyl compounds include bishydroxyphenyl sulfone, methylphenyl sulfone, diphenyldisulfone and the like. The addition amount of the other cyclic acid anhydride, phenols, organic acids or sulfonyl compounds is preferably 0.05 to 20 mass% with respect to the total solid mass of the image forming layer, and 0.1 to 1
5 mass% is more preferable, and 0.1-10 mass% is the most preferable.

Further, for the purpose of expanding the stability of processability under developing conditions, a siloxane compound as described in EP 950517, JP-A-11-28809.
Fluorine-containing monomer copolymers such as those described in JP-A-3 can be added. As the siloxane-based compound, a block copolymer of dimethylsiloxane and polyalkylene oxide is preferable.
Made by Chisso Corporation, DBE-224, DBE-621, DBE
-712, DBP-732, DBP-534, German Teg
Polyalkylene oxide-modified silicone such as Tego Glide 100 manufactured by O Co. may be mentioned. The amount of the surfactant used, based on the total solid content of the image forming layer, 0.
05 to 15 mass% is preferable, and 0.1 to 5 mass% is more preferable.

In the image forming layer, after heating by exposure,
A printout agent for obtaining a visible image or a dye or pigment as an image colorant can be added immediately. Examples of the printing-out agent include a combination of a compound that generates an acid when heated by exposure to light and an organic dye that can form a salt. Specifically, combinations of o-naphthoquinonediazide-4-sulfonic acid halogenide and a salt-forming organic dye described in JP-A-50-36209 and JP-A-53-8128, and JP-A- 53-36223, JP-A-54
-74728, JP-A-60-3626, JP-A-61
The combination of a trihalomethyl compound and a salt-forming organic dye described in JP-A-143748, JP-A-61-151644 and JP-A-63-58440. As the trihalomethyl compound, there are an oxazole compound and a triazine compound, both of which have excellent stability over time and give a clear printout image. As the image colorant, for example, other dyes can be used in addition to the salt-forming organic dye, and for example, oil-soluble dyes and basic dyes are suitable.

Specifically, Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 6.
03, oil black BY, oil black BS, oil black T-505 (above, manufactured by Orient Chemical Industry Co., Ltd.), Victoria Pure Blue, crystal violet (CI. 42555), methyl violet (CI. 42535). , Ethyl violet, rhodamine B (CI. 145170B), malachite green (CI. 42000), methylene blue (CI.
52015) and the like. In addition, JP-A-6
The dyes described in JP-A-2-293247 are particularly preferable. The amount of the various dyes added is preferably 0.01 to 10% by mass, based on the total mass of the solid content of the image forming layer.
-3 mass% is more preferable.

If desired, a plasticizer may be added for the purpose of imparting flexibility to the coating film. Examples of the plasticizer include butylphthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, and acrylic. Examples thereof include oligomers and polymers of acid or methacrylic acid.

If necessary, the following various additives can be added. For example, onium salts, o-quinonediazide compounds, aromatic sulfone compounds, aromatic sulfonic acid ester compounds, and other compounds that are thermally decomposable and substantially reduce the solubility of the alkaline water-soluble polymer compound in the undecomposed state can be used. Can be used together. Addition of the compound is preferable from the viewpoint of improving the dissolution inhibiting ability of the image area in the developing solution. Examples of the onium salts include diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts, arsonium salts and the like. Among them, for example SI Schlesinger,
Photogr. Sci. Eng., 18, 387 (1974), TSBal et al,
Polymer, 21, 423 (1980), the diazonium salt described in JP-A-5-158230, U.S. Pat. No. 4,069,
055, 4,069,056, and JP-A-3-140.
Ammonium salt described in No. 140, DC Necker et a
l, Macromolecules, 17, 2468 (1984), CS Wen et a
l, The Proc. Conf. Rad. Curing ASIA, p478 Tokyo, O
ct (1988), US Pat. Nos. 4,069,055 and 4,
069,056 phosphonium salt, JV Criv
elloet et al. Macromolecules, 10 (6), 1307 (1977),
Chem. & Eng. News, Nov. 28, p. 31 (1988), European Patent 104,143, US Patents 339,049, 410,201, JP-A-2-150848, JP-A-2-150848. 2-296514, iodonium salts,

JV Crivello et al, Polymer J. 17, 7
3 (1985), JV Crivello et al, J.Org. Chem., 43,
3055 (1978), W. R, Watt et al, J. Polymer Sci., Po
lymerChem. Ed., 22, 1789 (1984), JV Crivello et
al, Polymer bull., 14, 279 (1985), JV Crivello
et al, Macromolecules, 14 (5), 1141 (1981), JVCr
ivello et al, J. Polymer Sci., Polymer Chem. Ed.,
17. 2877 (1979), European Patent Nos. 370,693 and 2
33,567, 297,443, 297,44
No. 2, US Pat. Nos. 4,933,377 and 3,90.
2,114, 410,201, 399,049
No. 4, ibid. 4,760,013, ibid. 4,734,444
No. 2,833,827, German Patent No. 2,904,
No. 626, No. 3,604,580, No. 3,604,5
No. 81, a sulfonium salt,

JV Crivello et al, Macromolecules,
10 (6), 1307 (1977), JV Crivelloet al, J. Polymer
Sci., Polymer Chem. Ed., 17, 1047 (1979), selenonium salt, CS Wen et al, The Proc. Conf. R
Examples include arsonium salts described in ad. Curing ASIA, p.478, Tokyo, Oct (1988). Of the above, diazonium salts are preferable, and among them, JP-A-5-158230.
The one described in the publication is more preferable.

As the counter ion of the onium salt, tetrafluoroboric acid, hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid, 5-nitro-o-toluenesulfonic acid, 5
-Sulfosalicylic acid, 2,5-dimethylbenzenesulfonic acid, 2,4,6-trimethylbenzenesulfonic acid, 2
-Nitrobenzenesulfonic acid, 3-chlorobenzenesulfonic acid, 3-bromobenzenesulfonic acid, 2-fluorocaprylnaphthalenesulfonic acid, dodecylbenzenesulfonic acid, 1-naphthol-5-sulfonic acid, 2-methoxy-4-hydroxy-5- Examples thereof include benzoyl-benzenesulfonic acid and paratoluenesulfonic acid. Of these, alkylaromatic sulfonic acids such as hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid, and 2,5-dimethylbenzenesulfonic acid are preferable.

Examples of the o-quinonediazide compound include
Compounds having at least one o-quinonediazide group, which increase alkali solubility by thermal decomposition, can be mentioned, and compounds having various structures can be used. Said o
-Quinonediazide helps the solubility of the lithographic printing plate precursor by both effects of losing the ability to inhibit the dissolution of the binder by thermal decomposition and changing the o-quinonediazide itself into an alkali-soluble substance.

Examples of the o-quinonediazide compound as described above include those described in J. 33, "Light-Sensitive Systems" by John Coley, John Wiley & Sons. Inc.
Although the compounds described on pages 9 to 352 can be used, sulfonic acid esters or sulfonic acid amides of o-quinonediazide reacted with various aromatic polyhydroxy compounds or aromatic amino compounds are preferable. Further, benzoquinone (1,2) -diazide sulfonic acid chloride described in JP-A-43-28403 or US Pat. Nos. 3,046,120 and 3,188,210.
Also preferred are the esters of benzoquinone- (1,2) -diazide sulfonic acid chloride or naphthoquinone- (1,2) -diazide-5-sulfonic acid chloride described in US Pat.

Further, esters of naphthoquinone- (1,2) -diazide-4-sulfonic acid chloride with phenol formaldehyde resin or cresol-formaldehyde resin, naphthoquinone- (1,2) -diazide-4-sulfonic acid chloride and pyrogallol. Esters with acetone resins are also preferred. Others, for example, JP-A-4
7-5303, JP-A-48-63802, JP-A-4.
8-63803, JP-A-48-96575, JP-A-49-38701, JP-A-48-13354, JP-B-41-11222, JP-B-45-9610, JP-B-49-17481, US Pat. No. 2,797,213
No. 3, No. 3,454, 400, No. 3, 544, 32
No. 3, No. 3,573,917, No. 3,674,4
95, 3,785,825, British Patents 1,2
No. 27,602, No. 1,251,345, No. 1,
Those described in 267,005, 1,329,888, 1,330,932, German Patent 854,890 and the like are also useful. These compounds may be used alone or in combination of several kinds. The addition amount of the onium salt, o-quinonediazide compound, aromatic sulfonic acid ester or the like is preferably 0.1 to 50% by mass with respect to the total solid mass of the image forming layer,
0.5-30 mass% is more preferable, and 0.5-20 mass% is the most preferable.

In addition, for the purpose of enhancing the discrimination of images and the resistance to scratches on the surface, as described in Japanese Patent Application Laid-Open No. 2000-187318, a polymer having a carbon number of 3 to 20 is used. It is preferable to use a polymer having a (meth) acrylate monomer having 2 or 3 fluoroalkyl groups as a polymerization component. The addition amount is preferably 0.1 to 10% by mass, and more preferably 0.5 to 5% by mass, based on the total mass of the solid content of the image forming layer. Further, for the purpose of imparting resistance to scratches, a compound that lowers the coefficient of static friction of the surface can be added. Specific examples thereof include esters of long-chain alkylcarboxylic acids as disclosed in US Pat. No. 6,117,913. The addition amount thereof is preferably 0.1 to 10% by mass, and more preferably 0.5 to 5% by mass, based on the total mass of the solid content of the image forming layer. Further, various dissolution inhibitors may be included for the purpose of adjusting the solubility of the image forming layer. As a dissolution inhibitor, JP-A-11
A disulfone compound or a sulfone compound described in JP-A-119418 is preferably used, and 4,4′-bishydroxyphenylsulfone is preferably used as a specific example. The addition amount thereof is preferably 0.05 to 20% by mass, more preferably 0.5 to 10% by mass, based on the total solid content of the image forming layer.

As a specific example of a photosensitive lithographic printing plate to which the plate-making method of the present invention can be applied, a lithographic printing method in which an image forming layer as disclosed in Japanese Patent Application No. 2000-378507 is used as a positive heat-sensitive layer having a two-layer structure. The original edition is also included. That is, this positive-type heat-sensitive layer has a laminated structure and comprises a heat-sensitive layer provided at a position close to the surface (exposed surface) and a lower layer containing an alkali-soluble polymer compound provided on the side closer to the support. It is characterized by having. The above-mentioned (A) infrared absorbing dye, (B) alkali-soluble polymer compound, (C) alkali-soluble polymer compound which is compatible with the above-mentioned (A) infrared-absorbing dye, in one or both of the heat-sensitive layer and the lower layer. It is possible to include a compound, which reduces the solubility of the compound in an alkaline aqueous solution and reduces the solubility-decreasing action by heating, and other components. As the alkali-soluble polymer compound used in the lower layer, an acrylic resin can maintain good solubility of the lower layer in an alkali developing solution containing a buffering organic compound and a base as main components, and therefore, during development. Is preferable from the viewpoint of image formation. Further, the acrylic resin having a sulfamide group is particularly preferable. Further, as the alkali-soluble polymer compound used in the heat-sensitive layer, a strong hydrogen bonding property is generated in the unexposed area,
In the exposed area, a resin having a phenolic hydroxyl group is desirable because some hydrogen bonds are easily released. More preferably, it is a novolac resin. The infrared absorbing dye can be added not only to the heat-sensitive layer but also to the lower layer. The lower layer can also function as a heat-sensitive layer by adding an infrared absorbing dye to the lower layer. When the infrared absorbing dye is added to the lower layer, the same materials as those in the upper heat-sensitive layer may be used, or different materials may be used. Other additives may be contained only in the lower layer,
It may be contained only in the heat sensitive layer, or may be contained in both layers.

The image forming layer (including the above-mentioned two-layer structure) of the lithographic printing plate precursor can be coated on a suitable support by dissolving each of the above components in a solvent. Examples of the solvent include ethylene dichloride, cyclohexanone, methyl ethyl ketone, methanol, ethanol, propanol, ethylene glycol monomethyl ether, 1-methoxy-2.
-Propanol, 2-methoxyethyl acetate, 1-
Methoxy-2-propylacetate, dimethoxyethane, methyl lactate, ethyl lactate, N, N-dimethylacetamide, N, N-dimethylformamide, tetramethylurea, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, α-butyrolactone, toluene, etc. However, the present invention is not limited to these. The above solvents may be used alone or in combination of two or more.

When the image-forming layer has a two-layer structure, it is preferable to select those having different solubilities with respect to the alkali-soluble polymer compound used for the heat-sensitive layer and the alkali-soluble polymer compound used for the lower layer. That is, after applying the lower layer, when applying a heat-sensitive layer that is the upper layer adjacent to it, if a solvent capable of dissolving the alkali-soluble polymer compound of the lower layer is used as the coating solvent for the uppermost layer, the mixing at the layer interface will occur. It cannot be ignored, and in extreme cases, it may become a uniform single layer instead of multiple layers. Therefore, the solvent used for coating the upper heat-sensitive layer is preferably a poor solvent for the alkali-soluble polymer compound contained in the lower layer.

When the image forming layer is applied, the total solid concentration of the above components in the solvent is generally preferably 1 to 10% by mass. The dry coating amount (solid content) of the image forming layer formed by coating and drying the support is generally 0.5.
It is preferably up to 5.0 g / m ² . When using a two-layer structure,
The heat sensitive layer is 0.05 to 1.0 g / m ² , and the lower layer is 0.
It is preferably ³ to 3.0 g / m ² . As the coating amount decreases, the apparent sensitivity increases, but the film characteristics of the image forming layer deteriorate. The method for coating on the support can be appropriately selected from various known methods,
Examples thereof include bar coater coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, grade coating and roll coating. A surfactant such as the fluorine-based surfactant described in JP-A-62-170950 may be added to the coating liquid for the image forming layer for the purpose of improving the coatability. The amount added is 0.0 with respect to the total solid content of the image forming layer.
1-1 mass% is preferable, and 0.05-0.5 mass% is more preferable.

—Support— Examples of the support for the lithographic printing plate precursor include a pure aluminum plate, an aluminum alloy plate, and a plastic film on which aluminum is laminated or vapor deposited. The surface of the aluminum plate is preferably subjected to surface treatment such as graining treatment, permeation treatment with an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate or the like, or anodization treatment. In addition, after graining the aluminum plate described in US Pat. No. 2,714,066 and then dipping it in an aqueous solution of sodium silicate, the aluminum plate described in Japanese Patent Publication No. 47-5125 is anodized. An aluminum plate that has been immersed in an aqueous solution of an alkali metal silicate is also preferable.

As the anodizing treatment, for example, sulfuric acid,
Anodize an aluminum plate in an electrolytic solution of inorganic acid such as phosphoric acid, chromic acid, nitric acid, boric acid, etc., or organic acid such as oxalic acid, sulfamic acid, etc. Is applied by flowing an electrode. Also, US Pat. No. 3,65
The silicate electrodeposition described in the specification of No. 8,662 is also effective.

Also, US Pat. No. 4,087,341, JP-B-46-27481, and JP-A-52-3.
It is also useful that the support described in Japanese Patent No. 0503, which has been subjected to electrolytic graining, is subjected to the anodizing treatment. Aluminum sheets which have been grained, chemically etched and further anodized as described in US Pat. No. 3,834,998 are also useful. These treatments are performed for the purpose of making the surface of the support hydrophilic, for the purpose of preventing harmful reaction with the image forming layer provided on the support, and for improving the adhesion to the image-formed image. It is given for various purposes such as.

The lithographic printing plate precursor is one in which at least an image forming layer is laminated on a support, but an undercoat layer may be provided on the support if necessary. Examples of components used in the undercoat layer include various organic compounds,
For example, phosphonic acids having an amino group such as carboxymethyl cellulose, dextrin, gum arabic, and 2-aminoethylphosphonic acid; phenylphosphonic acid which may have a substituent, naphthylphosphonic acid, alkylphosphonic acid, glycerophosphonic acid, methylene Organic phosphonic acids such as diphosphonic acid and ethylenediphosphonic acid; phenylphosphoric acid which may have a substituent, naphthylphosphoric acid,
Organic phosphoric acid such as alkyl phosphoric acid and glycerophosphoric acid;
Organic phosphinic acids such as phenylphosphinic acid which may have a substituent, naphthylphosphinic acid, alkylphosphinic acid and glycerophosphinic acid; glycine and β-
Amino acids such as alanine; and hydrochlorides of amines having a hydroxyl group such as triethanolamine hydrochloride. The organic compounds may be used alone or in combination of two or more. It is also a preferable embodiment to undercoat the above-mentioned diazonium salt.

As the undercoat layer, the following general formula (II
An organic undercoat layer containing at least one organic polymer compound having a structural unit represented by I) is also preferable.

[0095]

In the formula, R⁵¹Is a hydrogen atom, a halogen atom or
Represents an alkyl group, R⁵²And R⁵³Each independently water
Elemental atom, hydroxyl group, halogen atom, alkyl group, substituted alkyl
Kill group, aryl group, substituted aryl group, -OR⁵⁴, -C
OOR⁵⁵, -CONHR⁵⁶, -COR⁵⁷Or-show CN
And the R⁵²And R⁵³Combine with each other to form a ring structure
May be. Where R⁵⁴~ R⁵⁷Each independently
Represents an aryl group or an aryl group. X is a hydrogen atom, a metal atom,
-NR⁵⁸R⁵⁹R⁶⁰R⁶¹Represents Where R⁵⁸~ R ⁶¹Is it
Each independently a hydrogen atom, an alkyl group, a substituted alkyl group,
Represents a reel group or a substituted aryl group, R⁵⁸And R⁵⁹Are mutual
They may be bonded to each other to form a ring structure. m is 1 to 3
Represents a number. The dry coating amount of the undercoat layer is 2 to 200 m
g / m²Is preferred, 5-100 mg / m²Is more preferred
Yes. This dry coating amount is 2 mg / m²Is less than enough
The film property may not be obtained. Meanwhile, 200 mg / m²To
Even if you apply more than that, you cannot get any further effect.
Yes.

The undercoat layer can be provided by the following method. That is, water or methanol, ethanol, an organic solvent such as an organic solvent such as methyl ethyl ketone or a mixed solvent thereof, a solution for the undercoat layer is applied on a support such as an aluminum plate, and a method for providing it by drying,
Water or an organic solvent such as methanol, ethanol, methyl ethyl ketone, or a mixed solvent thereof in a solution for the undercoat layer, a support such as an aluminum plate is immersed to adsorb the organic compound, and then water, etc. It is a method of washing and drying with.

In the former method, 0.000 of the organic compound is used.
It is preferable to use an undercoat layer solution having a concentration of 5 to 10% by mass. On the other hand, in the latter method, the concentration of the organic compound in the undercoat layer solution is suitably 0.01 to 20% by mass, preferably 0.05 to 10% by mass, and more preferably 0.1 to 10% by mass. Is about 5% by mass. The immersion temperature is preferably 20 to 90 ° C, more preferably 25 to 50 ° C. The immersion time is preferably 0.1 second to 20 minutes, and 2
Seconds to 1 minute are more preferable. For the undercoat layer solution, use a basic substance such as ammonia, triethylamine and potassium hydroxide or an acidic substance such as hydrochloric acid and phosphoric acid to adjust the pH to 1 to 12.
It can also be adjusted within the range. Further, a yellow dye may be added for the purpose of improving tone reproducibility.

The infrared-sensitive lithographic printing plate can be recorded by an infrared laser, recording by an ultraviolet lamp or thermal recording by a thermal head or the like. As the infrared laser, a laser emitting infrared rays having a wavelength of 700 to 1200 nm is preferable, and a solid laser or a semiconductor laser emitting infrared rays in the same wavelength range is more preferable.

The alkaline developing treatment solution (hereinafter also simply referred to as "developing solution") which can be used in the plate-making method of the present invention is an alkaline aqueous solution and can be appropriately selected from conventionally known alkaline aqueous solutions. . Examples of the alkaline aqueous solution include a developer containing an alkali silicate or non-reducing sugar and a base, and a pH range of 12.5 to 14.0 is suitable, and a pH range of 12.5-13.5 is more preferable. . The alkali silicate shows alkalinity when dissolved in water, and examples thereof include alkali metal silicates such as sodium silicate, potassium silicate, and lithium silicate, and ammonium silicate. The alkali silicate may be used alone or in combination of two or more.

The above alkaline aqueous solution is developed by adjusting the mixing ratio and concentration of silicon oxide SiO ₂ which is a silicate component and alkali oxide M ₂ O (M represents an alkali metal or ammonium group). The sex can be adjusted easily. Among the alkaline aqueous solutions, the mixing ratio of the silicon oxide SiO ₂ and the alkali oxide M ₂ O (Si
O ₂ / M ₂ O: molar ratio) is preferably 0.5 to 3.0,
The one of 1.0 to 2.0 is more preferable. Said SiO ₂ / M ₂ O
When the value is less than 0.5, the alkali strength increases, which may cause an adverse effect such as etching a general-purpose aluminum plate as a support for the lithographic printing plate precursor, and when it exceeds 3.0. However, the developability may decrease.

The concentration of alkali silicate in the developing solution is 1 to 10% by mass with respect to the mass of the alkaline aqueous solution.
Is preferable, 3-8 mass% is more preferable, 4-7 mass% is the most preferable. If this concentration is less than 1% by mass, developability and processing ability may be deteriorated, and if it exceeds 10% by mass, precipitates and crystals are likely to be formed, and further gelation is likely to occur during neutralization during waste liquid. , It may interfere with waste liquid treatment.

In the developer containing a non-reducing sugar and a base, the non-reducing sugar means a saccharide having no reducing property because it has no free aldehyde group or ketone group, and trehalose in which reducing groups are bonded to each other. Type oligosaccharides, glycosides in which reducing groups of saccharides and non-saccharides are bound, and sugar alcohols that are hydrogenated and reduced to sugars. In the present invention, any of these can be preferably used. Examples of trehalose-type oligosaccharides include saccharose and trehalose,
Examples of the glycoside include alkyl glycosides, phenol glycosides, mustard oil glycosides, and the like. Examples of sugar alcohols include D, L-arabit, rebit,
Examples include xylit, D, L-sorbit, D, L-unnit, D, L-idit, D, L-talit, zuricit, and alodulcit. Furthermore, maltitol obtained by hydrogenation of a disaccharide, a reduced form (reduced starch syrup) obtained by hydrogenation of an oligosaccharide, and the like can be preferably mentioned.

Of the above, sugar alcohols and saccharoses are preferable as the non-reducing sugars, and among them, D-sorbit, saccharose, and reduced starch syrup are more preferable because they have a buffering action in an appropriate pH range. These non-reducing sugars may be used alone or in combination of two or more, and their proportion in the developing solution is preferably 0.1 to 30% by mass, 1
-20 mass% is more preferred.

The alkali silicate or non-reducing sugar can be combined with an alkali agent as a base by appropriately selecting it from conventionally known substances. Examples of the alkaline agent include sodium hydroxide, potassium hydroxide, lithium hydroxide, trisodium phosphate, tripotassium phosphate,
Triammonium phosphate, disodium phosphate, dipotassium phosphate, diammonium phosphate, sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogen carbonate,
Examples thereof include inorganic alkali agents such as potassium hydrogen carbonate, ammonium hydrogen carbonate, sodium borate, potassium borate, ammonium borate, potassium citrate, tripotassium citrate, sodium citrate, and the like.

Further, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanol. Organic alkali agents such as amine, ethyleneimine, ethylenediamine and pyridine are also preferable. These alkaline agents may be used alone or in combination of two or more. Of these, sodium hydroxide and potassium hydroxide are preferable. The reason is that the pH can be adjusted in a wide pH range by adjusting the addition amount to the non-reducing sugar.
Further, trisodium phosphate, tripotassium phosphate, sodium carbonate, potassium carbonate and the like are preferable because they have a buffering effect.

[0107] alkali developing solution, as described above, the alkali silicate or nonreducing sugar, but using a developing solution containing a base, conventionally Li as a cation component ^+, N
In the case where a ⁺ , K ⁺ , NH ₄ ⁺ are used, and in particular, a system containing a large number of cations having a small ionic radius has high penetrability into the image forming layer and excellent developability, but it also dissolves in the image area to cause image defects. Cause Therefore, to increase the alkali concentration,
There is a certain limit, and it is necessary to set delicate liquid conditions in order to completely process the image forming layer (residual film) without causing defects in the image portion and in the non-image portion. It was However, by using a cation having a large ionic radius as the cation component, the permeability of the developing solution into the image forming layer can be suppressed, and the alkali concentration, that is, the developing property does not decrease, and It is possible to improve the dissolution inhibiting effect of the part. As the cation component, other cations can be used in addition to the above-mentioned alkali metal cations and ammonium ions.

It is necessary to add a surfactant to the above alkaline aqueous solution (developing solution). Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants. Nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene polystyryl phenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, glycerin fatty acid partial esters, sorbitan fatty acid moieties. Esters, pentaerythritol fatty acid partial esters, propylene glycol monofatty acid esters,

Sucrose fatty acid partial esters, polyoxyethylene sorbitan fatty acid partial esters, polyoxyethylene sorbitol fatty acid partial esters, polyethylene glycol fatty acid esters, polyglycerin fatty acid partial esters, polyoxyethylenated castor oils,
Polyoxyethylene glycerin fatty acid partial esters,
Suitable examples include fatty acid diethanolamides, N, N-bis-2-hydroxyalkylamines, polyoxyethylene alkylamines, triethanolamine fatty acid esters, and trialkylamine oxides.

Examples of the anionic surfactants include fatty acid salts, abietic acid salts, hydroxyalkanesulfonic acid salts, alkanesulfonic acid salts, dialkylsulfosuccinic acid ester salts, α-olefinsulfonic acid salts, linear alkylbenzenesulfonic acid salts, and branched salts. Chain alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkylphenoxy polyoxyethylene propyl sulfonates, polyoxyethylene alkyl sulfophenyl ether salts, N-methyl-N-oleyl taurine sodium salt, N-alkyl sulfosuccinic acid monoamide Sodium salt, petroleum sulfonates, sulfated tallow oil,
Sulfate ester salts of fatty acid alkyl esters, alkyl sulfate ester salts, polyoxyethylene alkyl ether sulfate ester salts,

Fatty acid monoglyceride sulfate ester salts,
Polyoxyethylene alkyl phenyl ether sulfate ester salts, polyoxyethylene styryl phenyl ether sulfate ester salts, alkyl phosphate ester salts, polyoxyethylene alkyl ether phosphate ester salts, polyoxyethylene alkyl phenyl ether phosphate ester salts, styrene / anhydrous Preferable examples include partially saponified products of maleic acid copolymers, partially saponified products of olefin / maleic anhydride copolymers, and naphthalenesulfonate formalin condensates.

Examples of the cationic surfactant include alkylamine salts, quaternary ammonium salts such as tetrabutylammonium bromide, polyoxyethylene alkylamine salts and polyethylene polyamine derivatives. Examples of the amphoteric surfactant include carboxybetaines, alkylaminocarboxylic acids, sulfobetaines, aminosulfates, imidazolines and the like. Among the above surfactants, those with "polyoxyethylene" can be read as polyoxyalkylenes such as polyoxymethylene, polyoxypropylene and polyoxybutylene, and these are also included in the above surfactants. It The concentration of the surfactant in the developer is preferably 0.001 to 10% by mass,
5 to 1 mass% is more preferable, and 0.01 to 0.5 mass% is the most preferable.

The following additives may be added to the alkaline developing solution for the purpose of further improving the developing performance. For example, N described in JP-A-58-75152
Neutral salts such as aCl, KCl and KBr, JP-A-58-1
Chelating agents such as EDTA and NTA described in JP-A-90952, and [C described in JP-A-59-121336].
complexes such as o (NH ₃ ) ₆ ] Cl ₃ , CoCl ₂ .6H ₂ O, sodium alkylnaphthalenesulfonate described in JP-A No. 50-51324, and n-tetradecyl-N, N.
^ Anionic or amphoteric surfactant such as dihydroxyethyl betaine, nonionic surfactant such as tetramethyldecynediol described in US Pat. No. 4,374,920, and described in JP-A-55-95946. P-
Cationic polymers such as methyl chloride quaternary compounds of dimethylaminomethyl polystyrene, JP-A-56-
An amphoteric polymer electrolyte such as a copolymer of vinylbenzyltrimethylammonium chloride and sodium acrylate described in JP-A-142528, JP-A-57-192951.
Inorganic lithium compounds such as lithium chloride described in JP-A-58-59444, organic Si, Ti described in JP-A-59-75255, and the like. Including organometallic surfactants,
Examples thereof include organic boron compounds described in JP-A-59-84241, and quaternary ammonium salts such as tetraalkylammonium oxide described in EP101010.

[0114]

The surface conditioning liquid before burning of the present invention has a low foaming property and is suitable for automated application by a spray circulation type processing machine or the like. By using the pre-burning surface-adjusting solution of the present invention for making a plate of a photosensitive lithographic printing plate, particularly for making an infrared-sensitive lithographic printing plate having an image forming layer containing an infrared absorber, to give a defect to an image area. Without leaving a residual film on the non-image area, or even if there is a slight residual film, it does not stain the printed matter finally, and it is possible to provide a highly sharp and clear image with excellent printing durability. Plate is achieved.
In the positive type / negative type infrared-sensitive lithographic printing plate, the developing property generally largely changes depending on the temperature of the developing solution. When the temperature of the developer is high, the developability of the non-image area is good, but film slippage occurs in the image area. When the temperature of the developer is low, the residual film is likely to remain in the non-image area.
By using the pre-burning surface-adjusting liquid of the present invention, the residual film in the non-image area as described above is improved and stains are less likely to occur.

[0115]

The present invention will be described in detail below with reference to examples.
However, the present invention is not limited to these. In addition,
All "%" in the examples represent "mass%". <Preparation of original plate for planographic printing plate> 0.3mm thick aluminum plate
The aluminum plate (material 1050) with trichlorethylene to remove it.
After greasing, nylon brush and 400 mesh pumice-
Grain this surface with a water suspension and wash it thoroughly with water.
did. After washing, wash the aluminum plate at 45 ° C with 25% water.
Immerse in an aqueous solution of sodium oxide for 9 seconds to perform etching
After rinsing with water, soak in 20% nitric acid solution for 20 seconds.
It was pickled and washed again with water. Etching of the grained surface at this time
Amount is about 3g / m ²Met. Next, this aluminum
Umium plate with 7% sulfuric acid as electrolyte, current density 15A / d
m ²DC current of 3g / m²After providing the anodic oxide coating of
It was washed with water and dried. This is a substrate (I).

[0116]

Examples 1-72 and Comparative Examples 1-2 Substrate (I) 30
It was treated with a 2.5% aqueous solution of sodium silicate at 10 ° C. for 10 seconds, the following coating solution for undercoat layer was applied, and dried at 80 ° C. for 15 seconds. The dry coating amount of the undercoat layer after drying is 15 mg / m.
^{Was 2} .

<Coating liquid for undercoat layer> The following copolymer P (molecular weight 28,000) 0.3 g 100 g of methanol 1 g water

[0118] The following coating solution for the image forming layer was applied onto the obtained support so that the dry coating amount was 1.8 g / m ² to obtain a positive lithographic printing plate precursor.

<Synthesis of Specific Copolymer> Synthesis Example (Specific Copolymer 1) 31.0 g (0.36 mol) of methacrylic acid was placed in a 500 ml three-necked flask equipped with a stirrer, a condenser and a dropping funnel.
39.1 g (0.36 mol) of ethyl chloroformate and 200 ml of acetonitrile were added, and the mixture was stirred while cooling with an ice water bath. Triethylamine 36.4 was added to this mixture.
g (0.36 mol) was added dropwise by a dropping funnel over about 1 hour. After completion of the dropping, remove the ice-water bath and let it stand at room temperature for 3
The mixture was stirred for 0 minutes. To this reaction mixture, 51.7 g (0.30 mol) of p-aminobenzenesulfonamide was added, and the mixture was stirred for 1 hour while warming to 70 ° C in an oil bath. After completion of the reaction, this mixture was put into 1 liter of water while stirring the water, and the resulting mixture was stirred for 30 minutes. The mixture is filtered to remove the precipitate, which is slurried with 500 ml of water and then the slurry is filtered,
The obtained solid was dried to obtain a white solid of N- (p-aminosulfonylphenyl) methacrylamide (yield 46.9 g).

Then, in a 20 ml three-necked flask equipped with a stirrer, a condenser and a dropping funnel, 4.61 g of N- (p-aminosulfonylphenyl) methacrylamide, (0.0192 mol) and 2.94 g of ethyl methacrylate ( 0.0258 mol), acrylonitrile 0.80 g (0.015 mol)
And 20 g of N, N-dimethylacetamide were added, and the mixture was stirred while heating at 65 ° C. in a hot water bath. To this mixture was added 0.15 g of "V-65" (manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was stirred under a nitrogen stream for 2 hours while maintaining the temperature at 65 ° C. The reaction mixture was further added with N- (p-aminosulfonylphenyl) methacrylamide 4.61 g, ethyl methacrylate 2.94 g, acrylonitrile 0.80 g, N, N-
A mixture of dimethylacetamide and 0.15 g of "V-65" was added dropwise by a dropping funnel over 2 hours. After the dropping was completed, the resulting mixture was further stirred at 65 ° C. for 2 hours. After the reaction was completed, 40 g of methanol was added to the mixture, the mixture was cooled, and the resulting mixture was added to 2 liters of water while stirring this water, the mixture was stirred for 30 minutes, and then the precipitate was taken out by filtration and dried. Gave 15 g of a white solid. The weight average molecular weight (polystyrene standard) of the specific copolymer was measured by gel permeation chromatography and found to be 53,000.

[0121] <Coating liquid for image forming layer>   0.4 g of the above-mentioned specific copolymer 1 [component (B)]   m, p-cresol novolac [(B) component] 0.6 g   (M / p ratio = 6/4, weight average molecular weight 8000,     Contains 0.5% unreacted cresol)   Cyanine dye A [(A + C) component] 0.1 g   Phthalic anhydride [(D) component] 0.05 g   p-toluenesulfonic acid 0.002 g   Ethyl violet 0.02g   (Counterion: 6-hydroxy-β-naphthalenesulfonic acid)   Naphthoquinone 1,2-diazide-5-sulfonylcroid     Esterification product with pyrogallol-acetone resin 0.01 g   Fluorine-based surfactant 0.05g   (Brand name: Megafac F-177, manufactured by Dainippon Ink and Chemicals, Inc.)   Methyl ethyl ketone 8g   1-methoxy-2-propanol 4g

[0122]

Examples 1 to 36 and Comparative Examples 1 and 2 (Preparation of SiO ₂ -Containing Alkali Developing Solution) Silicon oxide SiO ₂ and potassium oxide K ₂ O having a mixing ratio SiO ₂ / K ₂ O of 1.1. Potassium acidate 4.0%, Pionine C-158-G
(Made by Takemoto Yushi) 0.025%, PIONIN D-1105
(Made by Takemoto Yushi) 0.005% and Olfine AK-0
2 (manufactured by Nisshin Chemical Co., Ltd.) was used to prepare an alkali developing treatment solution containing 0.015%.

The lithographic printing plate precursor obtained as described above had an output of 500 mW and a wavelength of 830 nm and a beam diameter of 17 μm (1 / e).
The semiconductor laser of ² ) was used to perform exposure at a main scanning speed of 5 m / sec and the temperature was kept at 25 ° C. This lithographic printing plate precursor is an automatic processor PS900N in which the alkaline developing solution is filled.
P (manufactured by Fuji Photo Film Co., Ltd.)
The development processing was carried out at 12 ° C., 28 ° C., 30 ° C. for 12 seconds. After the development processing, a water washing step was performed.

The above plate was subjected to plate surface treatment with soybean polysaccharide or various aqueous solutions containing soybean polysaccharide and a sulfonate at a concentration shown in Tables 1 and 2 below (a surface conditioning solution before burning (1) to (36)). After burning at 270 ° C for 7 minutes, wash with water and gum G
The plate surface was processed with U-7 (1: 1) (manufactured by Fuji Photo Film Co., Ltd.) to obtain a lithographic printing plate on which plate making was completed (Examples 1 to 1).
36). On the other hand, Comparative Example 1 was prepared as in Example 1 except that a 2.5% aqueous solution of boric acid was used as the surface conditioning solution before burning. Further, Comparative Example 2 was prepared in the same manner as in Example 1 except that the pre-burning surface-adjusting solution and the burning treatment were not performed.

Pre-burning surface conditioning solution (1) shown in Tables 1 to 2
Details of the soybean polysaccharide and sulfonate used in (36) are as follows. Soybean Polysaccharide A: Soyafive-S-DN (made by Fuji Oil,
Galactose 46.1%, arabinose 22.6%, galacturonic acid 18.2%, crude protein 9.2%) Soybean polysaccharide B: Soyafive-S-LN (made by Fuji Oil,
Galactose 43.6%, arabinose 22.5%, galacturonic acid 2.2%, crude protein 10.4%)

Sulfonates (a) to (o)

[0127]

[Table 1]

[0128]

[Table 2]

These lithographic printing plates were evaluated as follows. The planographic printing plate was used to print on high-quality paper with a commercially available ink using a KOR type printer manufactured by Heidelberg. <Evaluation of balance of image area / non-image area> (Evaluation of developability of non-image area) The developability of the non-image area of the lithographic printing plate obtained as described above was determined by "presence or absence of residual film in non-image area". Sensory evaluation was performed by observing. The stains on the printed matter were also evaluated, and the results are shown in Tables 3 and 4. -Criteria- A: Sufficiently developed, no residual image forming layer on the non-image area was observed. There was no stain on the print. Δ: The image forming layer was slightly left on the non-image area. However, there was no stain on the printed matter. X: The image forming layer remained on the non-image area, and stains were generated on the printed matter.

(Evaluation of film slippage in image area) The "defect in image area" of the lithographic printing plate obtained as described above was measured according to the following criteria.
It was visually observed and sensory evaluation was performed. Also, the film slippage on the printed matter was evaluated, and the results are shown in Table 3. -Reference- ○: No defect was observed in the image area. There was no white spot in the image area on the printed matter. Δ: The image area density was slightly reduced, and some defects were recognized. However, there was no white spot in the image area on the printed matter. X: There is a defective portion in the image area. White spots were found in the image area on the printed matter. The evaluation results are summarized in Tables 3-4.

<Evaluation of Printing Durability> It is represented by the number of prints of a normal print until the image part is worn out and ink is not attached and a normal print cannot be obtained. The number of sheets with poor printing durability is small. The results are summarized in Tables 3-4. <Foamability> Tables 3 to 4 summarize the foamability in the treatment tank containing the surface conditioning solution before burning in the spray circulation type processor. -Standard- ○: No bubbles are generated. B: Bubbles are generated but there is no problem in use. X: There is a problem in use.

[0132]

[Table 3]

[0133]

[Table 4]

[0134]

Examples 37 to 72 and Comparative Examples 3 and 4 (Preparation of alkaline developing solution containing non-reducing sugar) Potassium salt of D-sorbit / potassium oxide K ₂ O in which non-reducing sugar and base are combined. 0%, Pionin C-158-G (manufactured by Takemoto Yushi) 0.025%, Pionin D-1105 (manufactured by Takemoto Yushi) 0.005%, and Olphin AK-02.
An alkaline developing treatment solution containing 0.015% (manufactured by Nissin Chemical Co., Ltd.) was prepared. Exposure, development and washing with water were carried out in the same manner as in Examples 1 to 36 and Comparative Examples 1 and 2 except that this alkaline developing solution was used. The plate was surface-treated with the surface conditioning solution (1) to (36) before burning, burned at 270 ° C. for 7 minutes, washed with water, and gum GU-7 (1: 1) (manufactured by Fuji Photo Film Co., Ltd.) The plate surface treatment was carried out to obtain a lithographic printing plate for which plate making was completed (Examples 37 to 72). On the other hand, Comparative Example 3 was prepared as in Example 37 except that a 2.5% aqueous solution of boric acid was used as the surface conditioning solution before burning. Further, as Comparative Example 4, a plate was prepared in the same manner as in Example 37, except that the pre-burning surface-adjusting solution and the burning process were not performed.
These planographic printing plates were evaluated in the same manner as in Examples 1-36. The results are summarized in Tables 5-6.

[0135]

[Table 5]

[0136]

[Table 6]

[0137]

Examples 73 to 108, Comparative Examples 5 and 6 Substrates (I) were coated with the following undercoat liquid and dried at 80 ° C. for 30 seconds. The coating amount after drying was 8 mg / m ² . (Undercoating liquid) Aminoethylphosphonic acid 0.1 g Methanol 70 g Pure water 30 g

Next, the following solution [A] was prepared. This solution is applied to the above-mentioned undercoated substrate (I), and 100 ° C. for 1 hour.
After drying for a minute, a negative lithographic printing plate precursor [A] was obtained. The coating amount after drying was 1.5 g / m ² . (Solution [A]) Diphenyliodonium trifluoromethanesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.15 g Infrared absorber (NK-2014, manufactured by Japan Photosensitive Dye Research Institute Co., Ltd.) 0.10 g Obtained from phenol and formaldehyde Novolac resin (weight average molecular weight 10000) 1.5 g Crosslinking agent (compound MM-1 represented by the following structural formula) 0.5 g Colorant (Vicotria Pure Blue manufactured by Hodogaya Chemical Co., Ltd.) 0.04 g Fluorosurfactant (Megafuck F-176, manufactured by Dainippon Ink and Chemicals, Inc.) 0.03 g methyl ethyl ketone 20 g 1-methoxy-2-propanol 7 g methyl alcohol 3 g

[0139]

The negative type lithographic printing plate precursor [A] obtained above had an output of 70 mW on the photosensitive material surface per 1 beam,
Image exposure was performed at a main scanning speed of 3.0 m / sec using a semiconductor laser having a wavelength of 830 nm and a beam diameter of 16 μm (1 / e ² ), and then preheating was performed at 140 ° C. for 1 minute.
This lithographic printing plate is an automatic processor PS9 filled with an alkaline water developer LH-DN (1: 7) manufactured by Fuji Photo Film Co., Ltd.
00NP (manufactured by Fuji Photo Film Co., Ltd.) was used for developing treatment at developer temperatures of 25 ° C, 30 ° C, 35 ° C and 12 seconds.
After the development processing, a water washing step was performed. Further, the plate surface is treated with the above-mentioned surface conditioning solution (1) to (36) before burning, and the plate is treated at 270 ° C. for 7 hours.
After burning for minutes, rinse with water, gum GU-7 (1: 1)
(Fuji Photo Film Co., Ltd.), the plate surface treatment was performed to obtain a lithographic printing plate for which plate making was completed (Examples 73 to 108). on the other hand,
Comparative Example 5 was prepared in the same manner as in Example 73 except that a 2.5% aqueous boric acid solution was used as the surface conditioning solution before burning.
Further, as Comparative Example 6, a plate was prepared in the same manner as in Example 73, except that the surface-polishing liquid before burning and the burning treatment were not performed.

These lithographic printing plates were evaluated as follows. The planographic printing plate was used to print on high-quality paper with a commercially available ink using a KOR type printer manufactured by Heidelberg.

<Evaluation of balance between image area / non-image area> (Evaluation of developability of non-image area) Non-image area of the lithographic printing plate obtained at the developer temperature of 25 ° C., 30 ° C. and 35 ° C. Sensory evaluation was performed on the developability of the image area by observing "presence or absence of residual film in non-image area" while changing the preheating temperature. Also, the stain on the printed matter was evaluated. -Reference- A: Sufficiently developed at a preheat temperature of 140 ° C, and no image forming layer remained on the non-image area. There was no stain on the print. Δ: At the preheating temperature of 140 ° C., the image forming layer was slightly left on the non-image area. However, there was no stain on the printed matter. Further, at the preheating temperature of 130 ° C., it was sufficiently developed and no image forming layer remained on the non-image area. There was no stain on the print. X: The image forming layer remained on the non-image area even at the preheating temperature of 130 ° C., and the printed matter was stained.

(Evaluation of the film thickness of the image area) The film thickness of the image area of the lithographic printing plate at the developer temperatures of 25 ° C., 30 ° C. and 35 ° C. obtained as described above was changed by changing the preheating temperature. The "defect in the image area" was observed and sensory evaluation was performed. The film slippage on the printed matter was also evaluated. -Reference- ○: No defect was observed in the image area at the preheating temperature of 140 ° C. There was no white spot in the image area on the printed matter. Δ: The image density slightly decreased at the preheating temperature of 140 ° C.,
Some defects were found. However, there was no white spot in the image area on the printed matter. Further, at the preheating temperature of 150 ° C., no defect was found in the image area. There was no white spot in the image area on the printed matter. X: There is a defective portion in the image area even at a preheating temperature of 150 ° C. White spots were found in the image area on the printed matter.

In addition, evaluation of printing durability and foaming property was carried out in Example 1.
~ 72. The evaluation results are shown in Tables 7-8.

[0145]

[Table 7]

[0146]

[Table 8]

[0147]

Examples 109 to 144, Comparative Examples 7 and 8 Substrate (I)
Was coated with the following undercoat liquid and dried at 80 ° C. for 30 seconds.
The coating amount after drying was 10 mg / m ² .

On the undercoated substrate (I), Japanese Patent Publication No.
0.828 parts by mass of naphthoquinone-1,2-diazide-5-sulfonic acid ester of polyhydroxyphenyl obtained by the condensation product of acetone and pyrogallol described in Example 1 of 3-28403 gazette and novolac type m / 2.2 parts by mass of p-mixed cresol formaldehyde resin, 0.02 parts by mass of novolac type octylphenol formaldehyde resin, 0.08 parts by mass of phthalic anhydride, 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4 -Oxadiazole 0.04 parts by mass and crystal violet paratoluene sulfonate 0.03 parts by mass are dissolved in 20 parts by mass of methyl cellosolve acetate and 8 parts by mass of methyl ethyl ketone to prepare a photosensitive solution and spin coating. It was coated and dried by a machine to obtain a photosensitive plate having a photosensitive layer of ² g / m ² . Fuji Photo Film Co., Ltd. PS light (2K
It was exposed using a W metal halide lamp) and kept at 25 ° C.

This planographic printing plate is used by Fuji Photo Film Co., Ltd.
Development was performed for 12 seconds at a developer temperature of 25 ° C., 30 ° C. and 35 ° C. by an automatic processor PS900NP (manufactured by Fuji Photo Film Co., Ltd.) filled with alkaline water developer DP-4 (1: 8). . After the development processing, a water washing step was performed. Further, the plate surface is treated with the above-mentioned surface conditioning solution (1) to (36) before burning, and after burning at 270 ° C. for 7 minutes, washing with water and gum G
The plate surface was processed with U-7 (1: 1) (manufactured by Fuji Photo Film Co., Ltd.) to obtain a lithographic printing plate on which plate making was completed (Example 109).
~ 144). On the other hand, a plate made in the same manner as in Example 109 was used as Comparative Example 7 except that a 2.5% aqueous solution of boric acid was used as the surface conditioning solution before burning. In addition, the treatment with the surface conditioning liquid before burning and the burning treatment were not performed, and the other conditions were the same as those in Example
A plate produced in the same manner as in Comparative Example 8 was used.

These lithographic printing plates are evaluated as follows. Further, using these lithographic printing plates, high-quality paper was printed with a commercially available ink using a KOR type printer manufactured by Heidelberg. <Evaluation of balance of image area / non-image area> (Evaluation of developability of non-image area) The developability of the non-image area of the lithographic printing plate obtained as described above was determined by "presence or absence of residual film in non-image area". Sensory evaluation was performed by observing. Also, the stain on the printed matter was evaluated. -Criteria- A: Sufficiently developed, no residual image forming layer on the non-image area was observed. There was no stain on the print. Δ: The image forming layer was slightly left on the non-image area. However, there was no stain on the printed matter. X: The image forming layer remained on the non-image area, and stains were generated on the printed matter.

(Evaluation of film slippage in the image area) The "defect in the image area" of the lithographic printing plate obtained as described above was evaluated according to the following criteria.
It was visually observed and sensory evaluation was performed. The film slippage on the printed matter was also evaluated. -Reference- ○: No defect was observed in the image area. There was no white spot in the image area on the printed matter. Δ: The image area density was slightly reduced, and some defects were recognized. However, there was no white spot in the image area on the printed matter. X: There is a defective portion in the image area. White spots were found in the image area on the printed matter. The evaluation of printing durability and foaming property was performed in Example 1
~ 72. The evaluation results are shown in Tables 9-10.

[0152]

[Table 9]

[0153]

[Table 10]

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G03F 7/032 G03F 7/032 F term (reference) 2H025 AB03 AC01 AC08 AD01 AD03 CB43 CB52 CC20 FA10 FA17 FA28 FA29 2H096 AA07 BA16 BA20 EA04 GA08 HA01 HA02 JA04 2H114 AA04 AA24 BA01 BA10 DA03 DA21 DA34 DA41 DA42 DA52 DA53 DA59 EA03 EA05 EA08 GA01 GA21

Claims (5)

[Claims] 1. A surface smoothing solution before burning comprising soybean polysaccharide. 2. The method according to claim 1, further comprising a sulfonate.
The surface conditioning solution before burning as described. 3. A method of making a lithographic printing plate comprising exposing a photosensitive lithographic printing plate to light, developing it, treating it with an aqueous solution containing a soybean polysaccharide, and then performing a burning treatment. 4. An infrared-sensitive lithographic printing plate having an image-forming layer containing an infrared absorber is exposed to infrared rays, developed, treated with an aqueous solution containing soybean polysaccharide, and then subjected to a burning treatment. A method for making a lithographic printing plate. 5. An infrared-sensitive lithographic printing plate having an image-forming layer containing an infrared absorber is exposed to infrared rays, developed, and then treated with an aqueous solution containing soybean polysaccharide and sulfonate, and then burned. A method of making a lithographic printing plate comprising: