JP2001290285A - Alkali developing solution for planographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an alkali developing solution for a planographic printing plate capable of forming a high sharpness clear image without causing defects to the image area. SOLUTION: The alkali developing solution for a planographic printing plate with an image forming layer containing an IR absorbent contains a surfactant having a dialkylsiloxane group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a developing solution for alkali development of a lithographic printing plate precursor capable of making a plate directly by infrared laser scanning based on a digital signal from a computer or the like.

[0002]

2. Description of the Related Art In recent years, the development of lasers has been remarkable. In particular, solid-state lasers and semiconductor lasers having a light emitting region from near infrared to infrared have become easily available in high power and small size. These lasers are very useful as an exposure light source for a system for making a plate directly from digital data. As an image recording material suitable for laser writing, for example, JP-A-7-285275 discloses a binder such as a cresol resin, a substance that absorbs light to generate heat, and a thermally decomposable material such as quinonediazide. Further, a positive type image recording material containing a compound which can substantially reduce the solubility of the binder before decomposition is proposed. This is a substance (heat mode type) in which a substance that generates heat by absorbing the light in an exposed portion by infrared irradiation generates heat and makes the exposed portion alkali-soluble (heat mode type). Therefore, the thermal efficiency was low, and the solubility in an alkali developing solution in the developing step was not satisfactory. For this reason, the alkali concentration of the developer has been increased to ensure the solubility of the exposed portion.

However, the heat mode type lithographic printing plate precursor has low resistance to dissolution of the image portion in an alkali developing solution under the above-described high-concentration alkaline conditions, and the surface of the image recording material is slightly damaged. Melts only, and causes a defect in the image area. In particular, the tendency was more remarkable in a positive type lithographic printing plate precursor using a polymer compound having high solubility in an aqueous alkali solution. Therefore, there is a limit in increasing the alkali concentration of the alkali developing solution so that a residual film does not occur in a non-image portion, and it is difficult to form a sharp and clear image without giving a defect to a formed image portion. Met. In particular, in a fine image including a dot portion, a thin line, and the like, it is required that the sharpness and the reproducibility be improved.

[0004]

SUMMARY OF THE INVENTION The present invention solves the conventional problems and provides an alkali developing solution for a lithographic printing plate capable of forming a sharp and clear image without giving a defect to an image portion. The purpose is to do.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies on components capable of improving the dissolution inhibiting power of the image area. It has been found that the alkali solubility of a part can be reduced, and the present invention has been completed. Therefore, the present invention
The present invention relates to an alkali developing solution for a lithographic printing plate having an image forming layer containing an infrared absorbing agent, wherein the alkali developing solution contains a surfactant having a dialkylsiloxane group.

In this specification, a plate making method using the above-mentioned alkali developing solution will be described. As a lithographic printing plate precursor, using a lithographic printing plate precursor having an image forming layer containing at least an infrared absorber on a support, irradiating the lithographic printing plate precursor with an infrared laser based on digital data to obtain a desired image. Upon exposure, the laser light is efficiently absorbed by the infrared absorber, and an image is formed through the following process. That is, in the case of a positive type lithographic printing plate precursor, only the exposed portion generates heat due to accumulation of absorbed energy due to exposure and becomes soluble in alkaline water, and the exposed portion is exposed by the developing process using the alkali developing solution of the present invention. In the case of a negative type lithographic printing plate precursor, only the exposed portion generates heat due to accumulation of absorbed energy due to exposure, and generates an acid. Causes a crosslinking reaction, while only the exposed areas become insoluble in alkaline water to form an image,
The non-exposed area is removed by a developing process using the alkali developing solution of the present invention, and a desired image is formed.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The alkali developing solution of the present invention will be described below. The alkali developing solution (hereinafter, also simply referred to as "developing solution") used for the developing process is an aqueous alkaline solution, and can be appropriately selected from conventionally known alkaline aqueous solutions. As the alkaline aqueous solution,
Examples thereof include a developer comprising an alkali silicate or a non-reducing sugar and a base, and particularly preferably a developer having a pH of 12.5 to 14.0. The alkali silicate exhibits 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 aqueous alkali solution is developed by adjusting the mixing ratio and concentration of silicon oxide SiO _{2 as} a component of silicate and alkali oxide M ₂ O (M represents an alkali metal or ammonium group). Sex can be easily adjusted. Among the aqueous alkali solutions, a 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 a 0.5 to 3.0,
Those having 1.0 to 2.0 are more preferable. The SiO ₂ / M ₂ O
If the value is less than 0.5, the alkali strength is increased, so that a harmful effect of etching a general-purpose aluminum plate or the like as a support for the lithographic printing plate precursor may occur. In some cases, the developability may decrease.

The concentration of the alkali silicate in the developer is 1 to 10% by mass based on the mass of the aqueous alkali solution.
Is preferably 3 to 8% by mass, and most preferably 4 to 7% by mass. If the concentration is less than 1% by mass, developability and processing capacity may be reduced. If the concentration is more than 10% by mass, precipitates and crystals are easily formed, and gelation tends to occur during neutralization at the time of waste liquid. In some cases, waste liquid treatment may be hindered.

[0010] In a developer comprising a non-reducing sugar and a base, the non-reducing sugar means a saccharide which does not have a reducing property because it has no free aldehyde group or ketone group. Type oligosaccharides, glycosides in which a reducing group of a saccharide is bonded to a non-saccharide, and sugar alcohols obtained by hydrogenating and reducing a saccharide are classified. In the present invention, any of these can be suitably used. Examples of trehalose-type oligosaccharides include saccharose and trehalose,
Examples of the glycoside include an alkyl glycoside, a phenol glycoside, and a mustard oil glycoside. As sugar alcohols, for example, D, L-arabit, rebit,
Xylit, D, L-sorbit, D, L-unnit, D, L-idit, D, L-tallit, zuricit, allozurcit, and the like. Furthermore, maltitol obtained by hydrogenation of a disaccharide, a reductant (reduced starch syrup) obtained by hydrogenation of an oligosaccharide, and the like can also be preferably mentioned.

Among the above, as the non-reducing sugar, sugar alcohols and saccharose are preferable, and among them, D-sorbitol, 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 the ratio in the developer is preferably 0.1 to 30% by mass, more preferably 1 to 30% by mass.
-20 mass% is more preferable.

The alkali silicate or non-reducing sugar can be combined with an alkali agent as a base by appropriately selecting it from conventionally known ones. Examples of the alkali 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, and ammonium borate, potassium citrate, tripotassium citrate, and sodium citrate.

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, pyridine and the like can also be suitably mentioned. These alkali agents may be used alone or in combination of two or more. Among them, sodium hydroxide and potassium hydroxide are preferred. The reason is that adjusting the amount of addition to the non-reducing sugar enables pH adjustment in a wide pH range.
Also, trisodium phosphate, tripotassium phosphate, sodium carbonate, potassium carbonate and the like are preferable since they themselves have a buffering action.

The alkali developing solution for a lithographic printing plate of the present invention contains a surfactant having a dialkylsiloxane group in the above-mentioned aqueous alkali solution. Examples of the surfactant having a dialkylsiloxane group include a dialkylpolysiloxane-based surfactant, particularly, a dimethylpolysiloxane-based surfactant. Specific examples include dimethylpolysiloxane-based surfactants such as poly (ethyleneoxy) siloxane and alkoxypoly (ethyleneoxy) siloxane represented by the following formula.

[0015]

(Wherein m, n, and s each represent an integer of 1 to 40, o is an integer of 1 to 30, p is an integer of 1 to 30, q is an integer of 1 to 30, r is 1 to 30) Represents an integer of 30;
R represents a hydrogen atom or a linear or branched alkyl group having 1 to 15 carbon atoms. Among them, preferred is poly (ethyleneoxy) siloxane. The surfactant having a dialkylsiloxane group used in the present invention also includes a surfactant modified by partially introducing a carboxylic acid group or a sulfonic acid group.

The above-mentioned dialkylpolysiloxane surfactants are generally available on the market. Examples of commercially available products include SM-5512 (manufactured by Toray Silicone), SH-200 (manufactured by Toray Silicone), and DB11.
0N (manufactured by Dow Corning), silicone X-20-250, X-
20-308, X-20-352, F-260, F-239, X-22-351, X-2
2-945, X-22-944, X-20-307 (manufactured by Shin-Etsu Chemical) and the like. The molecular weight of this surfactant is 100 to 1000
0 is preferable, 500 to 5000 is more preferable, and 10
00-3500 is most preferred. If the molecular weight is less than 100, it may not be possible to obtain a dissolution inhibiting power for the image area, and if it exceeds 10,000, the developability of the non-image area may be reduced.

The addition amount of the above surfactant is suitably 0.001 to 10% by mass in the alkali developing solution.
0.05-5 mass% is preferable. 0.1 to 3% by mass
Is most preferred. If the amount is less than 0.001% by mass, the solubility of the formed image area may not be sufficiently suppressed. On the other hand, if the amount exceeds 10% by mass, the dissolution inhibiting power may be too strong to lower the development sensitivity. . By including the above surfactant in the alkali developing solution,
Even when a polymer compound having high solubility in an alkaline aqueous solution is used, or when the alkali concentration is increased, an image portion is dissolved and an image defect is not caused, and a sharp, sharp image with an edge tone can be formed. It is possible to reproduce a fine image including a dot portion and a thin line with high sharpness.

As described above, the alkali developing solution of the present invention uses a developing solution containing an alkali silicate or a non-reducing sugar and a base.
^{i +, Na +, K +} , NH 4 + is used, inter alia, in a system containing a large amount of small cation ionic radius, while the permeability to the image forming layer is higher excellent developability, dissolved to image section Image defects. Therefore, there is a certain limit in increasing the alkali concentration, and it is delicate to completely process the image without causing defects in the image area and leaving no image forming layer (remaining film) in the non-image area. The setting of the proper liquid condition was requested. However, as the cation component,
By using a cation with a large ionic radius,
It is possible to suppress the permeability of the developer into the image forming layer, and it is also possible to improve the effect of suppressing the dissolution of the image portion without lowering the alkali concentration, that is, the developability. As the cation component, other cations can be used in addition to the alkali metal cation and the ammonium ion.

The following additives can be added to the alkali developing solution of the present invention for the purpose of further improving the developing performance. For example, neutral salts such as NaCl, KCl and KBr described in JP-A-58-75152, chelating agents such as EDTA and NTA described in JP-A-58-90952, and JP-A-59-121336. Complexes such as [Co (NH ₃ ) ₆ ] Cl ₃ and CoCl ₂ .6H ₂ O described in JP-A-50-51324;
Anionic or amphoteric surfactants such as N, N-dihydroxyethylbetaine; nonionic surfactants such as tetramethyldecinediol described in U.S. Pat. No. 4,374,920; and JP-A-55-95946. Amphoteric such as cationic polymers such as quaternary compounds of methyl chloride of p-dimethylaminomethylpolystyrene described in JP-A-56-142, and copolymers of vinylbenzyltrimethylammonium chloride and sodium acrylate described in JP-A-56-142528 Polymer electrolyte, JP-A-57-192
No. 951, a reducing inorganic salt such as sodium sulfite, an inorganic lithium compound such as lithium chloride described in JP-A-58-59444, and an inorganic lithium compound described in JP-A-59-75255.
Patent Application Publication No. JP-A-59-84241, organic boron compounds described in JP-A-59-84241, and quaternary ammonium salts such as tetraalkylammonium oxides described in EP101010 And the like.

The alkali developing solution for a lithographic printing plate of the present invention is most suitable for developing a lithographic printing original plate having an infrared laser-sensitive type image forming layer, which will be described later. The present invention can be suitably applied to the development processing of an image recording material having an image forming layer containing a quinonediazide compound.

In recent years, an automatic developing machine for a printing plate material has been widely used, especially in the plate making and printing industries, in order to rationalize and standardize the plate making operation. This automatic developing machine generally includes a developing section and a post-processing section, and includes a device for transporting a printing plate material, each processing solution tank, and a spray device. The developing process is performed by spraying each pumped processing liquid from a spray nozzle. Recently, a method is also known in which a printing plate material is immersed and conveyed by a submerged guide roll or the like in a processing liquid tank filled with a processing liquid to perform processing. In such an automatic processing, the processing can be performed while replenishing each processing liquid with a replenisher according to the processing amount, the operating time, and the like.

In this case, by adding an aqueous solution having a higher alkali strength than the developing solution to the developing solution as a replenishing solution, a large amount of image forming materials can be processed without replacing the developing solution in the developing tank for a long time. In the case of using the alkali developing solution of the present invention, it is a preferable embodiment to adopt this replenishment system. As the replenisher, the alkali developing solution for lithographic printing plate of the present invention can be used as an aqueous solution having higher alkali strength than the developing solution.

The above-mentioned developer and developer replenisher may contain various surfactants other than those described above, if necessary, for the purpose of accelerating or suppressing the developing property, dispersing the developing residue, and enhancing the ink affinity of the printing plate image area. An agent or an organic solvent can also be added. As the surfactant, an anionic, cationic, nonionic or amphoteric surfactant is preferable, and as the organic solvent, benzyl alcohol or the like is preferable. It is also preferable to add polyethylene glycol or a derivative thereof, or polypropylene glycol or a derivative thereof. If necessary, an inorganic salt-based reducing agent such as hydroquinone, resorcinol, sodium or potassium sulfite or bisulfite, an organic carboxylic acid, an antifoaming agent, and a water softener can also be added.

The lithographic printing plate developed using the alkali developing solution and the replenisher of the present invention is a rinsing solution containing washing water or a surfactant, or a desensitizing solution containing gum arabic or a starch derivative. Post processing is performed. In this post-treatment, these treatment liquids can be used in various combinations. It is also possible to use a so-called disposable processing method in which processing is performed with a substantially unused developing processing solution.

Next, a lithographic printing plate to which the alkali developing solution of the present invention can be applied will be described. The lithographic printing plate precursor has an image forming layer on a support, and further has other layers as necessary. The image forming layer has (A) an infrared absorbent, and further has at least (B) A) an alkali-soluble polymer compound, (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 lowering effect by heating; (D) It contains a cyclic acid anhydride. In the case of a negative type lithographic printing plate precursor, since the exposed portion is cured to form an image portion, the image forming layer is further crosslinked with (E) a compound capable of generating an acid by heat and (F) an acid. It is configured to contain a crosslinking agent. Hereinafter, each component will be briefly described.

-(A) Infrared Absorber- An infrared absorber (hereinafter sometimes referred to as "(A)" component) has a function of converting absorbed infrared rays into heat. As the infrared absorber usable in the present invention,
In a wavelength region of 700 nm or more, preferably a wavelength of 750 nm or more
Dyes or pigments capable of absorbing infrared rays with high efficiency in a wavelength region of 1200 nm are preferable, and dyes or pigments having an absorption maximum in a wavelength region of 750 nm to 1200 nm are more preferable.

Examples of the dye material include commercially available dyes and known dyes described in literatures (eg, “Dye Handbook”, edited by The Society of Synthetic Organic Chemistry, published in 1970). Dyes such as dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinone imine dyes, methine dyes, cyanine dyes, squalylium dyes, pyrylium salts, metal thiolate complexes and the like can be mentioned.

Among them, for example, Japanese Patent Application Laid-open No. Sho 58-12524
No. 6, JP-A-59-84356, JP-A-59-202
No. 829, JP-A-60-78787, JP-A-58-173696, JP-A-58-1.
Methine dyes described in JP-A-81690, JP-A-58-194595, JP-A-58-112793, JP-A-58-112793, and
Naphthoquinone dyes described in JP-A-224793, JP-A-59-48187, JP-A-59-73996, JP-A-60-52940, JP-A-60-63744, and JP-A-58-112792. And squarylium dyes described in British Patent No. 434,875, and dihydroperimidine squarylium dyes described in US Patent No. 5,380,635.

Further, a near-infrared absorption sensitizer described in US Pat. No. 5,156,938 is also preferable, and a substituted aryl benzo (thiol) described in US Pat. No. 3,881,924 is preferable. ) Pyrylium salts, JP-A-57-1426
No. 45 (U.S. Pat. No. 4,327,169), a trimethinethiapyrylium salt described in JP-A-58-1810.
No. 51, No. 58-220143, No. 59-41363
Nos. 59-84248, 59-84249, 59-146063 and 59-146061; pyrylium compounds described in JP-A-59-216146; cyanine dyes described in JP-A-59-216146; U.S. Pat. Nos. 283,475 and pentamethine thiopyrium salts, and the pyrylium compounds described in JP-B-5-13514 and 5-19702; commercially available products include Epolight III-178, E
polight III-130, Epolight III-125, Epolight
IV-62A (Eporin) and the like are also preferable.

Further, near infrared absorbing dyes represented by formulas (I) and (II) described in US Pat. No. 4,756,993 can also be mentioned as suitable ones. Of the above, cyanine dyes, squarylium dyes, pyrylium salts, and nickel thiolate complexes are more preferred.

Examples of the pigment include commercially available pigment or color index (CI) handbook, “Latest Pigment Handbook” (edited by Japan Pigment Technical Association), published in 1977, “Latest Pigment Application Technology” (CMC Publishing, 1986). And “Printing Ink Technology” (CMC Publishing, 1984), for example, black pigment, yellow pigment, orange pigment, brown pigment, red pigment, purple pigment, blue pigment, green pigment, Examples include fluorescent pigments, metal powder pigments, and other polymer-bound dyes.

Specifically, for example, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelated azo pigments, phthalosinine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, Isoindolinone pigments, quinophthalone pigments, dyed lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments,
Examples include inorganic pigments and carbon black. Among them,
Carbon black is preferred.

The pigment may be used without being subjected to a surface treatment, or may be used after being subjected to a surface treatment. As a method of surface treatment, a method of surface coating a resin or wax,
Examples include a method of attaching a surfactant, and a method of bonding a reactive substance (for example, a silane coupling agent, an epoxy compound, or a polyisocyanate) to the pigment surface.
These methods of surface treatment are described in "Properties and Applications of Metallic Soaps"
(Koshobo), "Printing ink technology" (CMC Publishing, 198)
4th year) and "Latest Pigment Application Technology" (CMC Publishing, 19
1986).

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

The method for dispersing the pigment can be appropriately selected from known dispersing techniques such as a general-purpose dispersing machine for producing ink and toner. 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 disperser,
Examples include a KD mill, a colloid mill, a dynatron, a three-roll mill, and a pressure kneader. 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, based on the total 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 preferred. If the content is less than 0.01% by mass, the sensitivity may be lowered. If the content is more than 50% by mass, the uniformity of the image forming layer may be reduced 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. If you want another layer,
It is preferable to add it to a layer adjacent to a layer containing the component (C) described below. 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-An alkali-soluble polymer compound that can be used (hereinafter, referred to as "
It may be referred to as “component (B)”. As), an alkali water-soluble polymer compound having the following acidic groups (1) to (3) in the structure of the main chain and / or the side chain 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 are shown below, but the present invention is not limited to these.

(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. , M- / p-mixed cresol and condensation polymer of formaldehyde, phenol and cresol (m
Any of-, p- or m- / p- mixture may be used. ) And formaldehyde, and a novolak resin or a condensation polymer of pyrogallol and acetone. Further, a polymer compound obtained by polymerizing a monomer having a phenol group in a side chain can also be used.

As the high molecular compound having a phenolic hydroxyl group in the side chain, a polymerizable monomer composed of a low molecular compound having at least one unsaturated bond capable of polymerizing with the phenolic hydroxyl group is homopolymerized, A polymer compound obtained by copolymerizing a monomer with another polymerizable monomer is exemplified. Examples of the monomer having a phenol group in the side chain include acrylamide, methacrylamide, acrylate, methacrylate or hydroxystyrene having a phenol group in the 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.

The alkali-soluble compound having a phenol group
The mass average molecular weight of the polymer compound is 5.0 × 10^Two
~ 2.0 × 10^FiveHas a number average molecular weight of 2.0
× 10 ^Two~ 1.0 × 10^FiveAre preferred in terms of image forming properties.
New In addition, an alkali-soluble polymer having a phenol group
Sub-compounds may be used alone or in combination of two or more.
They may be used together. If combined, use US special
As described in U.S. Pat. No. 4,123,279,
Condensed polymer of t-butylphenol and formaldehyde
Of octylphenol and formaldehyde
An alkyl group having 3 to 8 carbon atoms as a substituent
With a condensation polymer of phenol and formaldehyde
May be used. These condensation polymers also have a mass average molecular weight.
5.0 × 10^Two~ 2.0 × 10^FiveHaving a number average molecular weight of 2.0
× 10^Two~ 1.0 × 10^FiveAre preferred.

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

[0044]

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 , R
¹⁶ represents an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, an arylene group or an aralkylene group which may have a substituent. R ³ , R ⁷ and R ¹³ are
Each independently represents a hydrogen atom, 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 ⁶ and R ¹⁷ each independently have 1 to 12 carbon atoms which may have a substituent.
Represents an alkyl group, a cycloalkyl group, an aryl group, and 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 have a single bond or a carbon number of 1 to 12 which may have a substituent.
Represents an alkylene group, 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 a polymer 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 structural unit, in one molecule,
An active imide group represented by the following formula and a monomer composed of a low-molecular compound having at least one polymerizable unsaturated bond are homopolymerized, or obtained by copolymerizing the monomer with another polymerizable monomer. High molecular compounds can be mentioned.

[0048]

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

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

The alkali-soluble polymer compound is a copolymer comprising a monomer structural unit having any one of the acidic groups (1) to (3) and a structural unit of another polymerizable monomer. In this case, the copolymer preferably contains at least 10 mol% of a monomer structural unit having any one selected from the acidic groups (1) to (3).
More preferably, the content is 0 mol% or more. When the content of the monomer constitutional unit is less than 10 mol%, sufficient alkali solubility cannot be obtained, and the development latitude may be narrow. 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 above acidic groups (1) to (3) is copolymerized with a polymerizable monomer having a constitutional unit. As other polymerizable monomers, for example, the following monomers (a) to (1) can be exemplified, but the present invention is not limited thereto.

(A) Acrylic esters and methacrylic 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 acrylates such as acrylates; (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 methacrylates 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-acryloylacrylamide,
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;

Regarding the alkali water-soluble polymer compound, irrespective of a homopolymer or a copolymer, in terms of film strength,
Mass average molecular weight of 2,000 or more, number average molecular weight of 500
The above is preferable, and the weight average molecular weight is 5000 to 3
00000, the number average molecular weight is 800 to 250,000, and the degree of dispersion (mass average molecular weight / number average molecular weight) is 1.1 to
Ten are more preferred. Further, the alkali-soluble polymer compound is a phenol-formaldehyde resin,
In the case of a cresol-aldehyde resin or the like, those having a mass average molecular weight of 500 to 20,000 and a number average molecular weight of 200 to 10,000 are preferred.

The content of the above-mentioned alkaline water-soluble polymer compound is from 30 to 30% based on the total solid content of the image forming layer.
99 mass% is preferable, 40-95 mass% is more preferable, and 50-90 mass% is most preferable. The content is
If the amount is less than 30% by mass, the durability of the image forming layer may decrease. If the amount exceeds 99% by mass, the sensitivity and the durability may decrease. The polymer compound may be used alone or in combination of two or more.

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

Further, the above-mentioned solubility-suppressing effect on the alkali-soluble polymer compound disappears by heating. However, when the infrared absorbent itself is a compound that decomposes by heating, sufficient energy for the decomposition can be obtained by the laser output or the like. If it is not given by various conditions such as irradiation time, the action of suppressing the solubility of the alkali-soluble polymer compound cannot be sufficiently reduced, 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), for example, in consideration of the interaction with the (B) alkali-soluble polymer compound, for example,
It can be appropriately selected from compounds capable of interacting with the alkali-soluble polymer compound, such as a sulfone compound, an ammonium salt, a phosphonium salt, and an amide compound.
In particular, for example, when a novolak resin is used alone as the component (B), the “(A + C) component” described below is used.
Are preferable, and the cyanine dye A exemplified below is more preferable. The (A + C) component will be described later.

The mixing ratio (C / B) of the component (C) and the alkali-soluble polymer compound (B) is generally 1 /
99 to 25/75 is preferred. The mixing ratio is 1/99
When the amount is less than the above, that is, when the amount of the component (C) is too small, the interaction with the alkali-soluble polymer compound becomes insufficient, so that the alkali-solubility cannot be reduced and the image cannot be formed well. If the ratio exceeds / 75, that is, if the component (C) is too large, the interaction becomes excessive,
Sensitivity may be significantly reduced.

-Component (A + C)-In place of the components (A) and (C), a compound having both properties ((A + C) component) can be used. The component (A + C) has a property of absorbing light to generate heat (that is, the characteristic of the component (A)),
It is a basic dye which has an absorption range in the wavelength region of 00 to 1200 nm and is further compatible with an alkali-soluble polymer compound. The component (A + C) has, in its molecule, a group that interacts with an alkali-soluble polymer compound such as an ammonium group or an iminium group (that is, the property of the component (C)). And its alkali solubility can be suppressed. Examples of the component (A + C) include compounds represented by the following general formula (Z).

[0063]

In the general formula (Z), R ^{21 to} R ²⁴ each independently represent a hydrogen atom or an optionally substituted alkyl, alkenyl, alkoxy or cycloalkyl group having 1 to 12 carbon atoms. 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. R ^{21 to} R ²⁴ include, for example, a hydrogen atom,
Examples 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, examples of the substituent include 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 R ^{25 to} R ³⁰ include, for example, a methyl group, Examples 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, examples of the substituent include a halogen atom, a carbonyl group,
Examples include a nitro group, a nitrile group, a sulfonyl group, a carboxyl group, a carboxylic acid ester, and a sulfonic acid ester.

[0066] In the formula, R ³¹ to R ³³ each independently represents a hydrogen atom, a halogen atom, or an optionally substituted alkyl group having 1 to 8 carbon atoms, wherein R ^32, said R ³¹ or may be bonded to R ³³ to form a ring structure, m> 2, the general may be bonded multiple R ³² together form a ring structure. Examples of R ^{31 to} R ³³ include a chlorine atom, a cyclohexyl group, and a cyclopentyl ring and a cyclohexyl ring formed by bonding R ^{32 to} each other, 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,
Carboxylic acid esters, sulfonic acid esters and the like can be mentioned. M represents an integer of 1 to 8, and preferably 1 to 3.

[0067] In the formula, R ³⁴ to R ³⁵ each independently represent a hydrogen atom, a halogen atom, or an optionally substituted alkyl group having 1 to 8 carbon atoms, wherein R ³⁴ is a R ³⁵ A bond may form a ring structure, and when m> 2, a plurality of R ³⁴ may bond with each other to form a ring structure. As the R ³⁴ to R ^35, for example, a chlorine atom, a cyclohexyl group, a cyclopentyl ring R ³⁴ together is attached, cyclohexyl ring and the like, 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, and a sulfonic acid ester. Also, m
Represents an integer of 1 to 8, and among them, 1 to 3 is preferable.

[0068] 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, 2,4,4 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 And toluene sulfonic acid. Among them, alkyl aromatic 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 following compounds are preferably used, but in the present invention, the compounds are not limited to these. Not something.

When the component (A + C) having both of these properties is used instead of the component (A) and the component (C), the usage ratio of the component (A + C) to the component (B) [ (A + C) / (B)] is 1/99 to 30
/ 70 is preferable, and 1/99 to 25/75 is more preferable.

-(D) Cyclic Acid Anhydride- For the lithographic printing plate precursor, a cyclic acid anhydride is further used.
The cyclic acid anhydride has a bond conjugated to the carbonyl group of the carboxylic acid anhydride in its structure, controls the decomposition rate by increasing the stability of the carbonyl group, and decomposes at an appropriate rate during storage. To generate acid. Therefore, deterioration of the developability over time can be suppressed, and the developability can be stably maintained for a long period of time. As the cyclic acid anhydride, the following general formula (I)
Or the compound represented by (II) is mentioned.

[0072]

In the general formula (I), R ⁴¹ and R ⁴² are each independently a hydrogen atom or an alkyl, alkenyl, alkoxy or cycloalkyl group having 1 to 12 carbon atoms which may have a substituent. 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 be linked to each other to form a ring structure.
R ⁴¹ and R ⁴² preferably include, for example, 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 include a dodecyl group, a naphthyl group, a vinyl group, an allyl group, and 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 ester, a nitro group, and a nitrile group.

In the general formula (II), R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁴⁶
Are each independently a hydrogen atom, a hydroxy group, a halogen atom such as chlorine, a nitro group, a nitrile group, or an alkyl group having 1 to 12 carbon atoms which may have a substituent, an alkenyl group, an alkoxy group, It represents an alkyl group, an aryl group, a carbonyl group, a carboxy group, a carboxylate group or the like. R ⁴³ , R ⁴⁴ , R ⁴⁵ , and R ⁴⁶ include, for example, a hydrogen atom, a halogen atom,
Preferable examples include an unsubstituted alkyl group, an alkenyl group and an aryl group having 6 to 12 carbon atoms, such as 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.

Examples of the cyclic acid anhydride include phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, 3-hydroxyphthalic anhydride,
3-methylphthalic anhydride, 3-phenylphthalic anhydride,
Preferable examples include trimetic anhydride, pyrometic anhydride, maleic anhydride, phenyl maleic anhydride, dimethyl maleic 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 more preferably 1 to 1% by mass based on the total solid content of the image forming layer.
0% by weight is most preferred. If 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 the 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. The acid generator increases the number of compounds that decompose when heated to 100 ° C. or more to generate an acid. As the generated acid,
It is preferably a strong acid having a pKa of 2 or less, such as sulfonic acid and hydrochloric acid. Examples of the acid generator include Japanese Patent Application No. 11-66.
No. 733. The amount of the acid generator added is 0.01 based on the total solid content of the image forming layer.
Is preferably from 50 to 50% by mass, more preferably from 0.1 to 40% by mass, and most preferably from 0.5 to 30% by mass.

-(F) Crosslinking Agent Cross-Linked by Acid- When the lithographic printing plate precursor is of a negative type, a cross-linking agent crosslinked by an acid (hereinafter sometimes simply referred to as "crosslinking agent") is used in combination. Examples of the crosslinking agent include the following. (I) an aromatic compound substituted with an alkoxymethyl group or a hydroxymethyl group (ii) a compound having an N-hydroxymethyl group, an N-alkoxymethyl group or an N-acyloxymethyl group (iii) an epoxy compound Nos. 10-53788 and phenol derivatives.

The amount of the crosslinking agent to be added is preferably from 5 to 80% by weight based on the total weight of the solids in the image forming layer, and is preferably 10 to 80% by weight.
-75 mass% is more preferable, and 20-70 mass% is most preferable. When the phenol derivative is used as a cross-linking agent, the amount of the phenol derivative to be added is preferably 5 to 70% by mass, more preferably 10 to 50% by mass, based on the total solid content of the image forming material. Details of the above various compounds are described in Japanese Patent Application No. 11-66733.

-Other Components- Various additives can be further added to the image forming layer of the lithographic printing plate precursor suitable for applying the alkali developing solution, if necessary. For example, known additives such as cyclic acid anhydrides, phenols, organic acids, and sulfonyl compounds can be used in combination for the purpose of improving sensitivity. As the cyclic acid anhydride, US Pat.
Tetrahydrophthalic anhydride as described in 5,128 Pat, hexahydrophthalic anhydride, 3,6-oxy - [delta ⁴ - tetrahydrophthalic anhydride, alpha-phenyl maleic anhydride, succinic anhydride, etc. anhydride pro mellitic acid Is mentioned. As phenols, 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.

The organic acids include those described in JP-A-60-8
No. 8942, JP-A-2-96755, and the like, there are sulfonic acids, sulfinic acids, alkyl sulfates, phosphonic acids, phosphoric esters, carboxylic acids, and the like. Sulfonic acid, dodecylbenzenesulfonic acid, p-toluenesulfinic acid, ethyl sulfate, phenylphosphonic acid, phenylphosphinic acid, phenyl phosphate, diphenyl phosphate, benzoic acid, isophthalic acid, adipic acid, p-toluic acid,
3,4-dimethoxybenzoic acid, phthalic acid, terephthalic acid, 4-cyclohexene-2,2-dicarboxylic acid, erucic acid, lauric acid, n-undecanoic acid, ascorbic acid and the like. Examples of the sulfonyl compounds include bishydroxyphenylsulfone, methylphenylsulfone, and diphenyldisulfone. The amount of the other cyclic acid anhydride, phenol, organic acid or sulfonyl compound to be added is preferably 0.05 to 20% by mass, and more preferably 0.1 to 1% by mass based on the total solid content of the image forming layer.
5 mass% is more preferable, and 0.1 to 10 mass% is most preferable.

For the purpose of expanding the stability of processability under development conditions, nonionic surfactants described in JP-A-62-251740 and JP-A-3-208514, and JP-A-59-121044. No., JP-A-4-1314
An amphoteric surfactant described in JP-A No. 9 and the like can be added. Examples of the nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan triolate, monoglyceride stearate, polyoxyethylene nonyl phenyl ether, and the like. Examples of the amphoteric surfactant include alkyl di (aminoethyl) glycine, alkyl polyaminoethyl glycine hydrochloride, 2-alkyl-N-carboxyethyl-N
-Hydroxyethyl imidazolinium betaine, N-tetradecyl-N, N-betaine type (for example, trade name: Amogen K, manufactured by Daiichi Kogyo Co., Ltd.) and the like. The amount of the nonionic surfactant or the amphoteric surfactant used is 0.05 to 15% based on the total solid content of the image forming layer.
% By mass, more preferably 0.1% by mass.

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

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 (all manufactured by Orient Chemical Industries, 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, Japanese Unexamined Patent Publication
The dyes described in JP-A-2-293247 are particularly preferred. The amount of the various dyes to be added is preferably 0.01 to 10% by mass, and more preferably 0.1 to 10% by mass based on the total solid content of the image forming layer.
~ 3 mass% is more preferred.

[0084] If necessary, a plasticizer may be added for the purpose of imparting flexibility or the like to the coating film. As the plasticizer, for example, butylphthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, acrylic Examples include oligomers and polymers of acid or methacrylic acid.

Further, the following various additives can be added as required. For example, onium salts, o-quinonediazide compounds, aromatic sulfone compounds, aromatic sulfonic acid ester compounds and the like, a compound that substantially reduces the solubility of the alkali water-soluble polymer compound in a thermally decomposable, undecomposed state. Can be used together. The addition of the compound is preferred from the viewpoint of improving the ability to inhibit the dissolution of the image area in the developer. Examples of the onium salt include diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts, and arsonium salts. Among them, for example, SI Schlesinger,
Photogr. Sci. Eng., 18, 387 (1974), TSBal et al,
Polymer, 21, 423 (1980), diazonium salts described in JP-A-5-158230, U.S. Pat. No. 4,069,
Nos. 055 and 4,069,056, JP-A-3-140
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); U.S. Pat.
No. 069,056, JV Criv
elloet et al. Macromolecules, 10 (6), 1307 (1977),
Chem. & Eng. News, Nov. 28, p. 31 (1988), European Patent No. 104,143, U.S. Patent Nos. 339,049 and 410,201, JP-A-2-150848, JP-A-2-150848. Iodonium salt described in 2-296514,

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), EP 370,693, 2
33,567, 297,443, 297,44
No. 2, U.S. Pat. Nos. 4,933,377 and 3,90
2,114, 410,201, 399,049
Nos. 4,760,013, 4,734,444
No. 2,833,827, German Patent No. 2,904,
626, 3,604,580, 3,604,5
No. 81, a sulfonium salt,

[0087] JV Crivello et al, Macromolecules,
10 (6), 1307 (1977), JV Crivelloet al, J. Polymer
Sci., Polymer Chem. Ed., 17, 1047 (1979), selenonium salts, CS Wen et al, The Proc. Conf.R
ad. Curing ASIA, p.478, Tokyo, Oct (1988). Of the above, diazonium salts are preferable, and among them, JP-A-5-158230
The ones described in the above-mentioned publication are more preferable.

As the counter ion of the onium salt, tetrafluoroboric acid, hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid, 5-nitro-o-toluenesulfonic acid,
-Sulfosatilylic 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, paratoluenesulfonic acid and the like can be mentioned. Among them, alkyl aromatic sulfonic acids such as hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid, and 2,5-dimethylbenzenesulfonic acid are preferable.

As the o-quinonediazide compound,
Compounds having at least one o-quinonediazide group, which increase the alkali solubility by thermal decomposition, include compounds having various structures. Said o
-The quinonediazide helps the solubility of the lithographic printing plate precursor due to both effects of losing the ability to suppress the dissolution of the binder by thermal decomposition and converting o-quinonediazide itself into an alkali-soluble substance.

Examples of the o-quinonediazide compound as described above include those described in J. Am. Lighter-Sensitive Systems, Coser (John Wiley & Sons. Inc.) 33rd
The compounds described on pages 9 to 352 can be used, and among them, sulfonic esters or sulfonic amides of o-quinonediazide reacted with various aromatic polyhydroxy compounds or aromatic amino compounds are preferable. Also, benzoquinone (1,2) -diazide sulfonic acid chloride or U.S. Pat. Nos. 3,046,120 and 3,188,210 described in JP-A-43-28403.
Also preferred are the esters of benzoquinone- (1,2) -diazidesulfonic acid chloride or naphthoquinone- (1,2) -diazido-5-sulfonic acid chloride described in the above-mentioned item with phenol formaldehyde resin.

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 resin are also preferred. In addition, for example,
7-5303, JP-A-48-63802, JP-A-Showa 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 Patent 2,797,213
No. 3,454,400, No. 3,544,32
No. 3, No. 3,573,917, No. 3,674, 4
No. 95, 3,785, 825 and British Patent Nos. 1, 2
No. 27,602, No. 1,251,345, No. 1,
Nos. 267,005, 1,329,888, 1,330,932, and German Patent Nos. 854,890 are also useful. These compounds may be used alone or as a mixture of several kinds. The amount of the onium salt, o-quinonediazide compound, aromatic sulfonic acid ester or the like to be added is preferably from 0.1 to 50% by mass based on the total solid content of the image forming layer.
The content is more preferably from 0.5 to 30% by mass, most preferably from 0.5 to 20% by mass.

-Support-Examples of the support for providing the image forming layer 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 grained,
Preferably, a surface treatment such as a permeation treatment into an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate or the like, or an anodization treatment is performed. Also,
U.S. Pat. No. 2,714,066 describes an aluminum plate grained and then immersed in an aqueous solution of sodium silicate. An aluminum plate immersed in an aqueous solution of a metal silicate is also preferable.

As the anodic oxidation treatment, for example, one or two or more of an aqueous solution or a non-aqueous solution of an inorganic acid such as phosphoric acid, chromic acid, nitric acid, boric acid or an organic acid such as oxalic acid or sulfamic acid or a salt thereof is used. The application is performed by flowing the electrodes in the combined electrolyte with the aluminum plate as the anode. U.S. Pat. No. 3,658,
The silicate electrodeposition described in Japanese Patent No. 662 is also effective.

Also, US Pat. No. 4,087,341, JP-B-46-27481, and JP-A-52-3 are disclosed.
The support described in Japanese Patent No. 0503 which has been subjected to the anodic oxidation treatment on a support provided with electrolytic grains is also useful. An aluminum plate that is grained, chemically etched, and then anodized as described in U.S. Pat. No. 3,834,998 is also useful. These treatments are performed for the purpose of making the surface of the support hydrophilic, for the purpose of preventing harmful reactions with the image forming layer provided on the support, and for the purpose of improving the adhesion with the image formed image. And so on.

The lithographic printing plate precursor can be produced by coating an image forming layer as a photosensitive layer on a desired support.
An undercoat layer may be provided on the support. Examples of components used for the undercoat layer include various organic compounds, for example, carboxylic acids having an amino group such as carboxymethylcellulose, dextrin, gum arabic, and 2-aminoethylphosphonic acid; phenyl which may have a substituent Organic phosphonic acids such as phosphonic acid, naphthylphosphonic acid, alkylphosphonic acid, glycerophosphonic acid, methylenediphosphonic acid and ethylenediphosphonic acid; phenylphosphoric acid, naphthylphosphoric acid, alkylphosphoric acid which may have a substituent and Organic phosphoric acids such as glycerophosphoric acid; organic phosphinic acids such as phenylphosphinic acid, naphthylphosphinic acid, alkylphosphinic acid and glycerophosphinic acid which may have a substituent; amino acids such as glycine and β-alanine; Amine hydrochloride, etc. Such as hydrochloric acid salts of amines having a hydroxyl group. The organic compounds may be used alone or in a combination of two or more. It is also a preferred embodiment to undercoat the above-mentioned diazonium salt.

The undercoat layer is represented by 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.

[0097]

In the formula, R ⁵¹ represents a hydrogen atom, a halogen atom or an alkyl group, and R ⁵² and R ⁵³ each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, and a substituted aryl group. Group, -OR ⁵⁴ , -C
Represents OOR ⁵⁵ , —CONHR ⁵⁶ , —COR ⁵⁷ or —CN, wherein R ⁵² and R ⁵³ may be bonded to each other to form a ring structure. Here, each represent R ⁵⁴ to R ⁵⁷ independently represent an alkyl group or an aryl group. X is a hydrogen atom, a metal atom,
It represents a ^{-NR 58 R 59 R 60 R 61} . Wherein intentioned R ⁵⁸ to R ⁶¹ each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group, R ⁵⁸ and R
⁵⁹ may combine with each other to form a ring structure. m is 1
Represents an integer of 3. The dry coating amount of the undercoat layer is 2
-200 mg / m < ² > is preferable, and 5-100 mg / m < ² > is more preferable. If the dry coating amount is less than 2 mg / m ² , sufficient film properties may not be obtained. 200 mg on the other hand
/ M ² , no further effect can be obtained.

The undercoat layer can be provided by the following method. That is, water or an organic solvent such as methanol, ethanol, methyl ethyl ketone or a mixed solvent thereof, or a solution for the undercoat layer obtained by dissolving the organic compound on a support such as an aluminum plate, a method of providing by drying, water or methanol In a solution for the undercoat layer in which the organic compound is dissolved in an organic solvent such as ethanol or ethyl ethyl ketone or a mixed solvent thereof, a support such as an aluminum plate is immersed in the support such as an aluminum plate, and the organic compound is adsorbed. It is a method of washing and drying.

In the former, 0.005 to 1 of the organic compound is used.
It is preferable to use a solution for an undercoat layer having a concentration of 0% by mass. On the other hand, in the latter, the concentration of the organic compound in the undercoat layer solution is preferably 0.01 to 20% by mass, and 0.05% by mass.
-5% by mass or more. The immersion temperature is 20
-90 ° C is preferred, and 25-50 ° C is more preferred. The immersion time is preferably from 0.1 to 20 minutes, more preferably from 2 seconds to 1 minute. The pH of the undercoat layer solution can be adjusted to a range of pH 1 to 12 using a basic substance such as ammonia, triethylamine or potassium hydroxide or an acidic substance such as hydrochloric acid or phosphoric acid. Also, a yellow dye can be added for the purpose of improving tone reproducibility.

The lithographic printing plate precursor to be developed with the alkali developing solution of the present invention is generally prepared by dissolving the above-mentioned various components (components (A) to (F) and other components) in a solvent and forming a coating solution for an image forming layer. This is applied to a desired support to prepare the support. 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, and 1-methoxy-2.
-Propyl acetate, dimethoxyethane, methyl lactate, ethyl lactate, N, N-dimethylacetamide,
N-dimethylformamide, tetramethyl glare, N-
Examples include, but are not limited to, methylpyrrolidone, dimethylsulfoxide, sulfolane, α-butyrolactone, toluene, and the like. The solvents may be used alone or in combination of two or more.

Various components (component (A)) in the solvent
To (F) and other components) as 1
~ 50 mass% is preferred. The dry coating amount (solid content) of the image forming layer formed by coating and drying on the support is generally preferably from 0.5 to 5.0 g / m ² . The method of coating on the support can be appropriately selected from various known methods, for example, bar coater coating, spin coating,
Examples include spray coating, curtain coating, dip coating, air knife coating, grade coating, and roll coating. As the coating amount decreases, the apparent sensitivity increases, but the film characteristics of the image forming layer deteriorate. To the coating solution for the image forming layer, a surfactant, for example, a fluorine-based surfactant described in JP-A-62-170950 can be added for the purpose of improving coating properties. The amount of addition is 0.
It is preferably from 01 to 1% by mass, more preferably from 0.05 to 0.5% by mass.

The lithographic printing plate precursor of the present invention can be recorded by an infrared laser, and can also be recorded by an ultraviolet lamp or thermally by a thermal head or the like. As the infrared laser, a laser that emits infrared light having a wavelength of 700 to 1200 nm is preferable, and a solid-state laser or semiconductor laser that emits infrared light having the same wavelength range is more preferable.

[0104]

The lithographic printing plate precursor having an image forming layer containing an infrared absorbing agent is treated with the alkali developing solution for lithographic printing plate of the present invention, whereby image defects are formed in the image area while maintaining the developing property. Without inviting, it is possible to form a sharp, sharp image with an edge tone.

[0105]

The present invention will be described below in detail with reference to examples.
However, the present invention is not limited to these. In addition,
All “%” in the examples represent “% by mass”. <Preparation of a lithographic printing plate precursor> 0.3 mm thick aluminum
Wash the plate (material 1050) with trichlorethylene and remove
After grease, nylon brush and 400 mesh pumice-
Using a water suspension, grain this surface and wash it well with water
did. After washing, the aluminum plate was washed with 45% water at 45 ° C.
Etch for 9 seconds in an aqueous solution of sodium oxide
After washing with water, immerse in a 20% nitric acid aqueous solution for 20 seconds.
Pickled and washed again with water. Etching of the grained surface at this time
Approximately 3 g / m ^TwoMet.

Next, the aluminum plate was charged with 7% sulfuric acid.
Current density 15A / dm ^Two3g with direct current
/ M^TwoAfter providing an anodic oxide film, the substrate was washed with water and dried. This
This was treated with a 2.5% aqueous solution of sodium silicate at 30 ° C for 10 seconds.
And apply the following undercoat layer coating solution,
The support was obtained by drying for 5 seconds. Drying of the undercoat layer after drying
Application amount is 15mg / m^TwoMet.

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

[0108]

<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 in an ice water bath. To this mixture was added triethylamine 36.4.
g (0.36 mol) was dropped by a dropping funnel over about 1 hour. After dropping, remove the ice-water bath and allow
The mixture was stirred for 0 minutes. To the reaction mixture was added 51.7 g (0.30 mol) of p-aminobenzenesulfonamide, and the mixture was stirred for 1 hour while warming to 70 ° C. in an oil bath. After completion of the reaction, the mixture was added to 1 liter of water while stirring the water, and the resulting mixture was stirred for 30 minutes. The mixture was filtered to remove a precipitate, which was slurried with 500 ml of water, and then the slurry was filtered.
By drying the obtained solid, a white solid of N- (p-aminosulfonylphenyl) methacrylamide was obtained (yield 46.9 g).

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

The following coating solution for the image forming layer was applied on the obtained support so that the dry coating amount was 1.8 g / m ² , to obtain a positive type lithographic printing original plate. <Coating liquid for image forming layer> Specific copolymer 1 [component (B)] 0.4 g m, p-cresol novolak [component (B)] 0.6 g (m / p ratio = 6/4, weight) Average molecular weight 8000, contains 0.5% of 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 (counter ion: 6-hydroxy-β-naphthalenesulfonic acid) Esterified product of naphthoquinone 1,2-diazide-5-sulfonyl chloride and pyrogallol-acetone resin 0.01 g Fluorine surfactant 0.05 g (trade name: Megafac F-177, manufactured by Dainippon Ink and Chemicals, Inc.) Methyl ethyl ketone 8 g 1-methoxy-2-propanol 4 g

[0112]

EXAMPLES 1 TO 7 AND COMPARATIVE EXAMPLE 1 (Preparation of Alkaline Developing Solution Containing SiO ₂ ) Potassium Silicate with a Mixing Ratio of Silicon Oxide SiO ₂ and Potassium Oxide K ₂ O of SiO ₂ / K ₂ O of 1.1 Various siloxane compounds were added to 1 liter of a 4.0% aqueous solution in the amounts shown in Table 1 below to prepare alkali developing solutions (1) to (7) of the present invention. Comparative Example 1 having the above composition and containing no siloxane.

[0113]

EXAMPLES 8 to 14 and Comparative Example 2] (non-reducing sugars alkaline developing solution containing preparations) nonreducing sugar and a base and the combined D- sorbitol / potassium oxide K ₂ potassium salt 5.0 O consisting% Various siloxane compounds were added to 1 liter of the aqueous solution in the amounts shown in Table 1 below to prepare alkali developing solutions (8) to (14) of the present invention. Comparative Example 2 having the above composition and containing no siloxane was used.

Output 5 to the lithographic printing plate precursor obtained above
00 mW, wavelength 830 nm, beam diameter 17 μm (1 /
The semiconductor laser of e ² ) was exposed at a main scanning speed of 5 m / sec and kept at 25 ° C. This lithographic printing plate is
Automatic developing machine P filled with the above various alkali developing solutions
The film was developed with S900NP (manufactured by Fuji Photo Film Co., Ltd.) at a developing temperature of 25 ° C., 28 ° C., 30 ° C. for 12 seconds. After the development processing is completed, the gum (GU-7) is passed through a water washing step.
(1: 1)) to obtain a lithographic printing plate in which plate making was completed.

<Evaluation of balance between image area and non-image area> (Evaluation of developability of non-image area)
The sensory evaluation was performed on the lithographic printing plate obtained by developing at 25 ° C., 28 ° C., and 30 ° C. by observing “the presence or absence of a residual film in the non-image portion” of the non-image portion. The results are shown in Table 2 together with the evaluation of the stain on the printed matter. -Criterion- A: sufficiently developed, no residual image-forming layer on non-image area observed. There was no stain on the printed matter. Δ: The image forming layer was slightly left on the non-image portion. There was no stain on the printed matter. C: Defective development was observed, and the image forming layer remained in the non-image area. Smear occurred on printed matter.

(Evaluation of film loss in image area) The "defects in the image area" of the lithographic printing plate obtained by developing at 25.degree. C., 28.degree. C., and 30.degree. C. as described above were visually observed according to the following criteria. And sensory evaluation was performed. The evaluation results are shown in Table 2 below. -Criteria- A: No defect was observed in the image area. There was no whitening of the image area even on the printed matter. Δ: Image density slightly decreased, and some defects were observed. On the printed material, there was no whitening in the image area. X: The density of the image portion was significantly reduced, and there was a defective portion in the image portion. Color loss in the image area occurred on the printed matter.

[0117]

[Table 1]

Examples 1 to 7 and Comparative Example 1: Alkali developing solution containing SiO ₂ Examples 8 to 14 and Comparative Example 2: Alkali developing solution containing non-reducing sugar

[0119]

[Table 2]

Claims (1)

[Claims] 1. An alkali developing solution for a lithographic printing plate having an image forming layer containing an infrared absorbing agent, wherein the alkali developing solution contains a surfactant having a dialkylsiloxane group.