JP4675729B2 - Planographic printing plate precursor - Google Patents

Description

  The present invention relates to a lithographic printing plate precursor, and in particular, to a positive photosensitive lithographic printing plate precursor that can provide a lithographic printing plate that has excellent inking properties and that suppresses development debris generation in a developing bath. is there.

  The lithographic printing plate precursor has a configuration in which a recording layer comprising an image forming composition is provided on a support substrate. A typical manufacturing process is to apply an upper layer such as an image-forming composition dispersed or dissolved in an organic solvent and, if necessary, a protective layer on the surface of a support subjected to appropriate surface treatment, undercoating, back coating, etc. It is something to dry. Typical plate-making processes include contact exposure or projection surface exposure through an image mask, direct exposure by scanning and modulation of electromagnetic waves based on image information from a computer, and image forming composition on a support. After causing image-like physical property changes to the object, it is possible to remove (develop) the image-forming composition from the non-image area and perform treatments such as hydrophilization, oil sensitization, and protective film formation as necessary. A lithographic printing plate having a non-image area comprising a support surface layer and an image area comprising a hydrophobic composition surface layer is formed. In the lithographic printing plate thus obtained, in a typical printing process, the hydrophilic non-image area receives dampening water and the oleophilic image area receives ink, thereby forming an ink image on the surface. A printed matter can be obtained by transferring the obtained ink image directly or indirectly to a desired printing medium.

  As a recording layer (image forming layer) used in a lithographic printing plate precursor, a positive photosensitive layer using a heat mode process can be recorded directly from digital data and has no sensitivity to visible light. Useful. When such a recording layer is used, in order to form a good ink image on the surface, it is necessary to impart sufficient lipophilicity to the surface of the recording layer, and it is possible to improve ink adherence at the time of extrusion. This is useful because it leads to a significant increase in work efficiency during printing. However, if the surface is made oleophilic in order to improve the ink inking property, the developer penetration into the photosensitive layer is deteriorated, so that the developability is usually lowered. Therefore, it is preferable to use a material having a balance between hydrophilicity and oleophilicity in order to impart developability and inking property, but a material capable of sufficiently satisfying both hydrophilicity and oleophilicity is obtained. The current situation has not yet been obtained.

As a method for ensuring the lipophilicity of the recording layer, for example, a method using a polymer having a linear, branched or cyclic alkyl group having 4 to 20 carbon atoms such as phenolic hydroxyl group and stearyl group has been proposed (for example, , See Patent Document 1). However, when the above lipophilic polymer is used as the main component of the binder, since the amount added is large, the influence on other properties such as developability is increased, and it is difficult to use it. On the other hand, when such a lipophilic polymer is used in a small amount as an additive, there is a problem in that the effect of improving the ink deposition property as expected cannot be obtained.
In addition to the above, as a method for ensuring the lipophilicity of the recording layer, addition of a fluorosurfactant having a fluoroaliphatic group has also been proposed (see, for example, Patent Documents 2 and 3). However, a compound having a functional group containing a large number of fluorine atoms further has properties such as oil repellency, water repellency, and alkali development resistance. In addition, there are concerns that development debris and sludge are generated and sensitivity is lowered.
JP 2004-117882 A JP 2002-311577 A JP 2004-101893 A

  An object of the present invention is to provide a lithographic printing plate precursor that is excellent in ink deposition in the image area, that gives a good printed matter, and that suppresses the generation of precipitates in the developer even when continuously plate-making. Is to provide.

As a result of intensive studies, the present inventors have studied the constituent components of the polymer used as a binder, and found that the above problems can be solved by containing a polymer compound having a specific copolymerization component. It came to complete.
That is, the lithographic printing plate precursor according to the present invention comprises, on a support, (a) a monomer represented by the following general formula (1), (b) a monomer represented by the following general formula (2), and a carbon number of 20 or less. And a monomer selected from acrylic acid esters having a carbon number of 20 or less, and a polymer layer and a recording layer containing an infrared absorber as a copolymerization component.

In general formula (1), Rf is a fluoroalkyl group having 9 or more fluorine atoms or a perfluoroalkyl group-containing substituent, n represents 1 or 2, and R ¹ represents hydrogen or a methyl group. .

In the general formula (2), R ²¹ represents a hydrogen atom or a methyl group, and R ²² represents a divalent hydrocarbon group having an aliphatic cyclic structure having 3 to 30 carbon atoms. A represents an oxygen atom or —NR ²³ —, and R ²³ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.

Although the mechanism of action of the present invention is not clear, it is presumed as follows.
The polymer compound contained in the recording layer of the lithographic printing plate precursor according to the invention includes (b) a copolymer component having an aliphatic cyclic structure in the vicinity of the carboxylic acid represented by the general formula (2). a) Due to the function of the monomer component containing fluorine represented by the general formula (1), the polymer compound tends to be unevenly distributed on the surface. At this time, at the time of printing, due to the structure represented by (b) the general formula (2), the hydrophilic carboxylic acid group is shielded by the nearby aliphatic cyclic structure, and it is difficult to express hydrophilicity, Good ink landing property is developed on the surface of the recording layer. Further, in the developer, by being immersed in an excessive alkali developer, excellent solubility / dispersibility by the carboxylic acid group is expressed, but the aliphatic cyclic structure is introduced in the vicinity of the acid group. As a result, the vicinity of the acid group is bulky and the acid groups are unlikely to interact with each other. Therefore, the recording layer component in which the polymer diffuses in the developer, particularly the polymer compound, is less likely to aggregate, Development residue caused by precipitates and agglomerates, especially sludge that is difficult to process and easily adheres to the plate material, is suppressed, and the surface has excellent lipophilicity (thickness) and development in a developer. It is considered that the effect of suppressing the generation of scum and sludge is compatible.

  According to the present invention, an excellent ink-inking property in an image area is obtained, and a good printed matter can be obtained, and the occurrence of deposits such as development residue and sludge in the developer is suppressed even when the plate making process is continuously performed. A finished lithographic printing plate precursor can be obtained.

Hereinafter, the present invention will be described in detail.
The lithographic printing plate precursor according to the invention comprises: (a) a monomer represented by the following general formula (1); (b) a monomer represented by the general formula (2); and an acrylate ester having 20 or less carbon atoms. And a monomer selected from methacrylic acid esters having 20 or less carbon atoms, and a polymer compound having a copolymerization component (hereinafter referred to as a specific copolymer) and an infrared absorber. To do.

[ Selected from (a) a monomer represented by the general formula (1), (b) a monomer represented by the general formula (2), an acrylic ester having 20 or less carbon atoms and a methacrylic ester having 20 or less carbon atoms And a polymer compound having a monomer as a copolymerization component]
(A) a fluorine-containing monomer represented by the general formula (1) and (b) a carboxylic acid represented by the general formula (2), which are copolymer components that give preferable characteristics to the specific copolymer according to the present invention. The monomer having an aliphatic cyclic structure in the vicinity will be described in detail.
The fluorine-containing monomer used as the copolymerization component (a) in the present invention is represented by the following general formula (1).

In general formula (1), Rf is a fluoroalkyl group having 9 or more fluorine atoms or a perfluoroalkyl group-containing substituent, n represents 1 or 2, and R ¹ represents hydrogen or a methyl group. .
Specific examples of the fluorine atom-containing substituent in Rf include the following fluoroalkyl (meth) acrylates.
CH ₂ = CRCO ₂ (CH ₂ ) _m C _n F _{2n + 1}
(M represents 1 or 2, n represents an integer of 4 to 12, and R represents an alkyl group having 1 to 4 carbon atoms.)
CH ₂ = CRCO ₂ (CH ₂ ) _m (CF ₂ ) _n H
(M represents 1 or 2, n represents an integer of 4 to 12. R represents an alkyl group having 1 to 4 carbon atoms)
Here, in the fluoroalkyl group or perfluoroalkyl group represented by Rf, a recording layer having a fluorine atom concentration distribution in the film thickness direction is formed by using a fluorine atom group having 9 or more fluorine atoms. As the concentration distribution, a phenomenon occurs in which the fluorine concentration in the vicinity of the recording layer surface is high and the fluorine concentration is lowered in the depth direction of the recording layer. Especially, the thing of 9-30 is preferable for the number of the fluorine atoms per monomer unit, More preferably, it is 13-25. Within this range, the effect of orienting the specific copolymer on the surface is well expressed, and excellent inking properties are obtained. When the number of fluorine atoms contained in one unit is too large, there may be a case where the wearability is reduced due to the oil repellency of the fluorine atoms.
In addition, the fluorine atom content contained in the specific copolymer is 5 to 30 mmol / g from the viewpoint of improving the surface orientation of the specific copolymer and improving the development resistance and the inking property. The range of 8-25 mmol / g is more preferable. In addition, when the number of fluorine atoms contained in the copolymer is too large, there may be a case where the fleshing property is lowered due to the oil repellency of the fluorine atoms.

  The carboxyl group-containing monomer used as the copolymerization component (b) in the present invention is represented by the following general formula (2).

In the general formula (2), R ²¹ represents a hydrogen atom or a methyl group, and R ²² represents a divalent hydrocarbon group having an aliphatic cyclic structure having 3 to 30 carbon atoms. A represents an oxygen atom or —NR ²³ —, and R ²³ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.
R ²¹ in the general formula (2) represents a hydrogen atom or a methyl group, and a methyl group is particularly preferable.
As the divalent hydrocarbon group having an aliphatic cyclic structure having 3 to 30 carbon atoms as R ²² in the general formula (2), one or more cyclopropane, cyclo Pentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, dicyclohexyl, tercyclohexyl, norbornane, decahydronaphthalene, perhydrofluorene, tricyclo [5.2.2.6.6] decane, adamantane, quadricyclane, congressan, cubane , Spiro [4.4] octane, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclodecene, cyclohexadiene, cycloheptadiene, cyclooctadiene, cycloheptatriene, cyclodecatriene, cyclooctate Aliphatic cyclic structures such as ene, norbornylene, octahydronaphthalene, bicyclo [2.2.1] heptadiene, bicyclo [4.3.0] nonadiene, dicyclopentadiene, hexahydroanthracene, spiro [4.5] decadiene Examples thereof include those obtained by removing two hydrogen atoms on any carbon atom constituting the compound having a divalent hydrocarbon group. R ²² preferably has 3 to 30 carbon atoms including substituents.

(B) In the monomer represented by the general formula (2), the aliphatic cyclic structure represented by R ²² and the carboxyl group bonded thereto characterize the excellent inking property of the specific polymer of the present invention. That is, the hydrophilic cyclic group is sterically protected by the aliphatic cyclic structure, so that the hydrophilicity of the surface of the film made of the specific copolymer is lowered, and the inking property is improved by making it hydrophobic. Since the aliphatic cyclic structure has a three-dimensional structure as compared with the aromatic cyclic behavior, it is considered that the distance between the carboxyl group and the ring structure is closer and an effective shielding function is expressed.

Examples of the substituent that can be introduced into the divalent hydrocarbon group having an aliphatic cyclic structure represented by R ²² include a monovalent nonmetallic atomic group excluding hydrogen, and a halogen atom (—F, — Br, -Cl, -I), hydroxyl group, alkoxy group, aryloxy group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N -Alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N- Alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group, acylthio group, acylamido Group, N- alkylacylamino group, N- arylacylamino group, an aryl group, an alkenyl group, an alkynyl group and the like.
Hydrophobic substituents such as halogen atoms, hydrocarbon groups (alkyl groups, aryl groups, alkenyl groups, alkynyl groups), alkoxy groups, and aryloxy groups are more preferable because they tend to improve printing durability. If possible, these substituents may be bonded to each other or with a substituted hydrocarbon group to form a ring, and the substituent may be further substituted.

A is NR ²³ in the general formula (2) - R ²³ when it is, represents a monovalent hydrocarbon group having a hydrogen atom or 1 to 10 carbon atoms. Examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms represented by R ²³ include an alkyl group, an aryl group, an alkenyl group, and an alkynyl group.
Specific examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, isopropyl group, isobutyl group, sec-butyl group, 1 carbon number such as tert-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group, cyclohexyl group, 1-adamantyl group, 2-norbornyl group Up to 10 linear, branched or cyclic alkyl groups.
Specific examples of the aryl group include carbon having one heteroatom selected from the group consisting of an aryl group having 1 to 10 carbon atoms such as a phenyl group, a naphthyl group, and an indenyl group, a nitrogen atom, an oxygen atom, and a sulfur atom. Examples include heteroaryl groups of 1 to 10, such as furyl, thienyl, pyrrolyl, pyridyl, and quinolyl groups.
Specific examples of the alkenyl group include those having 1 to 10 carbon atoms such as vinyl group, 1-propenyl group, 1-butenyl group, 1-methyl-1-propenyl group, 1-cyclopentenyl group, 1-cyclohexenyl group and the like. A linear, branched, or cyclic alkenyl group is mentioned.
Specific examples of the alkynyl group include alkynyl groups having 1 to 10 carbon atoms such as ethynyl group, 1-propynyl group, 1-butynyl group, and 1-octynyl group. Examples of the substituent that R ²³ may have are the same as those described as the substituent that R ²² can introduce. The number of carbon atoms of R ²³ is 1 to 10 including the carbon number of the substituent.
A in the general formula (2) is preferably an oxygen atom or —NH— because synthesis is easy.
Although the preferable specific example of the repeating unit derived from the monomer represented by General formula (2) below is shown, this invention is not limited to these.

One type of repeating unit derived from the monomer represented by formula (2) may be contained in the binder polymer, or two or more types may be contained. The total content of the repeating unit derived from the monomer represented by the general formula (2) in the polymer of the present invention is appropriately determined depending on the structure, the design of the photosensitive layer, etc., but preferably the total mole of the specific copolymer component. It is contained in the range of 0.1 to 99 mol%, more preferably 1 to 80 mol%, still more preferably 5 to 60 mol%, based on the amount.
If the amount of carboxyl groups in the polymer is too small, sludge is generated in the developer, and if the amount is too large, the desired excellent inking property cannot be obtained. Therefore, the acid value per polymer is determined in terms of inking property and sensitivity. 0.01 to 3.0 mmol / g is preferable, 0.1 to 2.5 mmol / g is more preferable, and 0.2 to 2.0 mmol / g is more preferable.

In the polymer compound of the present invention, in addition to the structural units derived from the above-mentioned (a) and (b) two types of monomers, selected from acrylic acid esters having 20 or less carbon atoms and methacrylic acid esters having 20 or less carbon atoms However , other monomers may be copolymerized for various purposes such as improvement of coatability within the range not impairing the effects of the present invention.
As here can be used in combination of other monomers, e.g., acrylamide compounds, methacrylamide compounds, vinyl esters, styrenes, acrylonitrile, maleic anhydride, include known monomers such as maleic acid imide.

Examples of the acrylic esters that can be used as a copolymerization component in the polymer compound of the present invention include methyl acrylate, ethyl acrylate, (n- or i-) propyl acrylate, (n-, i-, sec-, or t). -) Butyl acrylate, amyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 5-hydroxypentyl acrylate, cyclohexyl acrylate, allyl acrylate, trimethylolpropane monoacrylate, Pentaerythritol monoacrylate, glycidyl acrylate, benzyl acrylate, methoxybenzyl acrylate, chlorobenzyl acrylate, 2- ( - hydroxyphenyl) ethyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, chlorophenyl acrylate, sulfamoylphenyl acrylate and the like.

Examples of the methacrylic acid ester that can be used as a copolymerization component in the polymer compound of the present invention include methyl methacrylate, ethyl methacrylate, (n- or i-) propyl methacrylate, (n-, i-, sec-, or t-). ) Butyl methacrylate, amyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, chloroethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 5-hydroxypentyl methacrylate, cyclohexyl methacrylate, allyl methacrylate, trimethylolpropane monomethacrylate, penta Erythritol monomethacrylate, glycidyl methacrylate, methoxybenzyl methacrylate, chlorobenzyl methacrylate DOO, 2-(p-hydroxyphenyl) ethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, chlorophenyl methacrylate, sulfamoylphenyl methacrylate and the like.

Examples of other acrylamides that can be used in combination include acrylamide, N-methylacrylamide, N-ethylacrylamide, N-propylacrylamide, N-butylacrylamide, N-benzylacrylamide, N-hydroxyethylacrylamide, N- Phenylacrylamide, N-tolylacrylamide, N- (p-hydroxyphenyl) acrylamide, N- (sulfamoylphenyl) acrylamide, N- (phenylsulfonyl) acrylamide, N- (tolylsulfonyl) acrylamide, N, N-dimethylacrylamide N-methyl-N-phenylacrylamide, N-hydroxyethyl-N-methylacrylamide and the like.

Examples of other methacrylamides that can be used in combination include methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-propylmethacrylamide, N-butylmethacrylamide, N-benzylmethacrylamide, N -Hydroxyethylmethacrylamide, N-phenylmethacrylamide, N-tolylmethacrylamide, N- (p-hydroxyphenyl) methacrylamide, N- (sulfamoylphenyl) methacrylamide, N- (phenylsulfonyl) methacrylamide, N -(Tolylsulfonyl) methacrylamide, N, N-dimethylmethacrylamide, N-methyl-N-phenylmethacrylamide, N-hydroxyethyl-N-methylmethacrylamide and the like.

Examples of vinyl esters that are other monomers that can be used in combination include vinyl acetate, vinyl butyrate, vinyl benzoate, and the like.
Examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, propyl styrene, cyclohexyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene, acetoxymethyl styrene, methoxy styrene, dimethoxy styrene, Examples include chlorostyrene, dichlorostyrene, bromostyrene, iodostyrene, fluorostyrene, carboxystyrene, and the like.
Among these monomers, bi- Niruesuteru, styrene, acrylonitrile is preferable.

Further, the recording layer in the lithographic printing plate precursor according to the invention may contain only one kind of the specific copolymer or a mixture of two or more kinds. As long as the effects of the present invention are not impaired, one or more fluorine-containing polymer compounds outside the scope of the present invention may be used in combination with the specific copolymer of the present invention as a mixture.
The fluorine-containing polymer compound used in combination is 0.01 to 300% by weight, preferably 0.1 to 250% by weight, more preferably 1 to 200% by weight, based on the total weight of the specific copolymer according to the present invention. Used in a range. As the fluorine-containing polymer compound that can be used in combination, commercially available ones can be used without limitation. Specifically, fluorine-based surfactants often used in the industry, JP-A-2002-311577, JP-A-2002-72474, Fluoropolymers described in JP-A Nos. 2004-101893 are preferably used.

The weight average molecular weight of the specific copolymer in the present invention is appropriately determined from the viewpoints of wall-thickness, developability, and generation of precipitates in the developer. Usually, when the molecular weight is increased, the inking property is excellent, but the developability is deteriorated, and the generation of precipitates and aggregates in the developer tends to increase. Conversely, when the molecular weight is low, developability and the generation of precipitates and aggregates in the developer are suppressed, but the inking property is lowered. The molecular weight is preferably 1,000 to 1,000,000, more preferably 2 from the viewpoint of the balance between the coating properties, the effect of improving the inking property, the handling property, the solvent solubility, and the uniformity during coating. The range is from 3,000 to 500,000, more preferably from 3,000 to 300,000.
Further, the specific copolymer according to the present invention may be linear, branched or have a block structure.

Hereinafter, the structure of the specific polymer compound [ (P-6) to (P-14), (P-17), (P-19) to (P-21)]] suitable for the present invention is represented by its weight average. Although illustrated with molecular weight (Mw), this invention is not restrict | limited to these.

  The content of the specific copolymer according to the present invention in the recording layer can be determined as appropriate, but it is usually contained at 0.0001 to 20% by mass with respect to the total weight of the nonvolatile components in the recording layer. More preferably, it is 0.001-15 mass%, More preferably, it is the range of 0.01-10 mass%.

[Infrared absorber]
For the recording layer of the lithographic printing plate precursor according to the invention, an infrared absorber (infrared absorbing dye or pigment) having an absorption maximum at a wavelength of 700 nm to 1200 nm is further used. The infrared absorber has a function of absorbing light energy irradiation rays such as an infrared laser used for recording and generating heat, and is useful from the viewpoint of improving recording sensitivity.

  As the dye, commercially available dyes and known dyes described in documents such as “Dye Handbook” (edited by the Society for Synthetic Organic Chemistry, published in 1970) can be used. Specifically, azo dyes, metal complex azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, metal thiolate complexes, oxonol dyes And dyes such as diimonium dyes, aminium dyes, and croconium dyes.

  Preferred dyes include, for example, cyanine dyes described in JP-A-58-125246, JP-A-59-84356, JP-A-59-202829, JP-A-60-78787, and the like. Methine dyes described in JP-A-58-173696, JP-A-58-181690, JP-A-58-194595, JP-A-58-112793, JP-A-58-224793, JP-A-59- 48187, JP-A 59-73996, JP-A 60-52940, JP-A 60-63744, etc., naphthoquinone dyes, JP-A 58-112792, etc. And cyanine dyes described in British Patent 434,875.

  Also, a near infrared absorption sensitizer described in US Pat. No. 5,156,938 is preferably used, and a substituted arylbenzo (thio) pyrylium salt described in US Pat. No. 3,881,924, Trimethine thiapyrylium salts described in JP-A-57-142645 (US Pat. No. 4,327,169), JP-A-58-181051, 58-220143, 59-41363, 59-84248 Nos. 59-84249, 59-146063, 59-146061, pyranlium compounds, cyanine dyes described in JP-A-59-216146, US Pat. No. 4,283,475 The pentamethine thiopyrylium salts described above and the pyrylium compounds disclosed in Japanese Patent Publication Nos. 5-13514 and 5-19702 are also preferably used. .

  Another example of a preferable dye is a near-infrared absorbing dye described as formulas (I) and (II) in US Pat. No. 4,756,993.

  Particularly preferred among these dyes are cyanine dyes, phthalocyanine dyes, oxonol dyes, squarylium dyes, pyrylium salts, thiopyrylium dyes, and nickel thiolate complexes. Furthermore, the dyes represented by the following general formulas (a) to (e) are preferable because of their excellent photothermal conversion efficiency. Particularly, the cyanine dyes represented by the following general formula (a) are used in the polymerizable composition of the present invention. In this case, it is most preferable because it gives high polymerization activity and is excellent in stability and economy.

In formula (a), X ¹ represents a hydrogen atom, a halogen atom, -NPh _2, X ² -L ¹ or a group shown below. Here, X ² represents an oxygen atom or a sulfur atom, and L ¹ represents a hydrocarbon group having 1 to 12 carbon atoms, an aromatic ring having a hetero atom, or a carbon atom having 1 to 12 carbon atoms including a hetero atom. Indicates a hydrogen group. In addition, a hetero atom here shows N, S, O, a halogen atom, and Se.

In the above formula, Xa ^- has Za described later ^- is defined as in, R ^a represents a hydrogen atom, an alkyl group, an aryl group, a substituted or unsubstituted amino group, substituted or unsubstituted amino group and a halogen atom.

R ¹ and R ² each independently represents a hydrocarbon group having 1 to 12 carbon atoms. From the storage stability of the recording layer coating solution, R ¹ and R ² are preferably hydrocarbon groups having 2 or more carbon atoms, and R ¹ and R ² are bonded to each other to form a 5-membered ring or It is particularly preferable that a 6-membered ring is formed.

Ar ¹ and Ar ² may be the same or different and each represents an aromatic hydrocarbon group which may have a substituent. Preferred aromatic hydrocarbon groups include a benzene ring and a naphthalene ring. Moreover, as a preferable substituent, a C12 or less hydrocarbon group, a halogen atom, and a C12 or less alkoxy group are mentioned. Y ¹ and Y ² may be the same or different and each represents a sulfur atom or a dialkylmethylene group having 12 or less carbon atoms. R ³ and R ⁴ may be the same or different and each represents a hydrocarbon group having 20 or less carbon atoms which may have a substituent. Preferred substituents include alkoxy groups having 12 or less carbon atoms, carboxyl groups, and sulfo groups. R ⁵ , R ⁶ , R ⁷ and R ⁸ may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 12 or less carbon atoms. From the availability of raw materials, a hydrogen atom is preferred. Za ⁻ represents a counter anion. However, Za ⁻ is not necessary when the cyanine dye represented by formula (a) has an anionic substituent in its structure and charge neutralization is not necessary. Preferred Za ⁻ is a halogen ion, a perchlorate ion, a tetrafluoroborate ion, a hexafluorophosphate ion, and a sulfonate ion, particularly preferably a perchlorate ion, a hexagonal salt, in view of the storage stability of the recording layer coating solution. Fluorophosphate ions and aryl sulfonate ions.

  Specific examples of the cyanine dye represented by formula (a) that can be suitably used in the present invention include those exemplified below, and paragraph numbers [0017] to [0019] of JP-A-2001-133969. And those described in paragraph numbers [0012] to [0038] of JP-A No. 2002-40638 and paragraph numbers [0012] to [0023] of JP-A No. 2002-23360.

In the general formula (b), L represents a methine chain having 7 or more conjugated carbon atoms, the methine chain may have a substituent, and the substituents are bonded to each other to form a ring structure. Also good. Zb ⁺ represents a counter cation. Preferred counter cations include ammonium, iodonium, sulfonium, phosphonium, pyridinium, alkali metal cations (Na ⁺ , K ⁺ , Li ⁺ ) and the like. R ^{9 to} R ¹⁴ and R ^{15 to} R ²⁰ are each independently a hydrogen atom or halogen atom, cyano group, alkyl group, aryl group, alkenyl group, alkynyl group, carbonyl group, thio group, sulfonyl group, sulfinyl group, oxy group Or a substituent selected from amino groups, or a combination of two or three of these, and may be bonded to each other to form a ring structure. Here, in the general formula (b), those in which L represents a methine chain having 7 conjugated carbon atoms and those in which R ^{9 to} R ¹⁴ and R ^{15 to} R ²⁰ all represent hydrogen atoms are easily available. From the viewpoint of the effect.

  Specific examples of the dye represented by formula (b) that can be suitably used in the present invention include those exemplified below.

In the general formula (c), Y ³ and Y ⁴ each represent an oxygen atom, a sulfur atom, a selenium atom, or a tellurium atom. M represents a methine chain having 5 or more conjugated carbon atoms. R ^{21 to} R ²⁴ and R ^{25 to} R ²⁸ may be the same or different, and are each a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a carbonyl group, a thiol group, Represents a group, a sulfonyl group, a sulfinyl group, an oxy group, or an amino group. Further, wherein Za ^- include a counter anion, Za in the general formula (a) ^- it is synonymous.

  In the present invention, specific examples of the dye represented by formula (c) that can be suitably used include those exemplified below.

In the general formula (d), R ²⁹ to R ³² each independently represent a hydrogen atom, an alkyl group, or an aryl group. R ³³ and R ³⁴ each independently represents an alkyl group, a substituted oxy group, or a halogen atom. n and m each independently represents an integer of 0 to 4. R ²⁹ and R ³⁰ , or R ³¹ and R ³² may be bonded to each other to form a ring, and R ²⁹ and / or R ³⁰ is R ³³ and R ³¹ and / or R ³² is R ³⁴ A ring may be bonded to each other, and when there are a plurality of R ³³ or R ³⁴ , R ³³ or R ³⁴ may be bonded to each other to form a ring. X ¹ and X ² are each independently a hydrogen atom, an alkyl group, or an aryl group, and at least one of X ¹ and X ² represents a hydrogen atom or an alkyl group. Q is a trimethine group or a pentamethine group which may have a substituent, and may form a ring structure together with a divalent organic group. Zc ⁻ represents a counter anion and has the same meaning as Za ⁻ in the general formula (a).

  In the present invention, specific examples of the dye represented by the general formula (d) that can be suitably used include those exemplified below.

In the general formula (e), R ^{35 to} R ⁵⁰ are each independently a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a hydroxyl group, or a carbonyl group that may have a substituent. Group, thio group, sulfonyl group, sulfinyl group, oxy group, amino group, and onium salt structure. M represents two hydrogen atoms or metal atoms, a halometal group, and an oxymetal group, and the metal atoms contained therein include IA, IIA, IIIB, IVB group atoms of the periodic table, first, second, second Three-period transition metals and lanthanoid elements can be mentioned, among which copper, magnesium, iron, zinc, cobalt, aluminum, titanium, and vanadium are preferable.

  In the present invention, specific examples of the dye represented by formula (e) that can be suitably used include those exemplified below.

  Examples of pigments used as infrared absorbers in the present invention include commercially available pigments and Color Index (CI) manual, “Latest Pigment Handbook” (edited by the Japan Pigment Technology Association, published in 1977), “Latest Pigment Applied Technology”. (CMC Publishing, published in 1986) and “Printing Ink Technology”, published by CMC Publishing, published in 1984).

  Examples of the pigment 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. Specifically, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelate azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments In addition, quinophthalone pigments, dyed lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, carbon black, and the like can be used. Among these pigments, carbon black is preferable.

  These pigments may be used without surface treatment, or may be used after surface treatment. The surface treatment method includes a method of surface coating with a resin or wax, a method of attaching a surfactant, a method of bonding a reactive substance (eg, silane coupling agent, epoxy compound, polyisocyanate, etc.) to the pigment surface, etc. Can be considered. The above-mentioned surface treatment methods are described in “Characteristics and Applications of Metal Soap” (Shobobo), “Printing Ink Technology” (CMC Publishing, 1984) and “Latest Pigment Application Technology” (CMC Publishing, 1986). Yes.

  The particle diameter of the pigment is preferably in the range of 0.01 μm to 10 μm, and preferably in the range of 0.05 μm to 1 μm, from the viewpoint of the stability of the dispersion in the recording layer coating liquid and the uniformity of the recording layer. More preferably, it is preferably in the range of 0.1 μm to 1 μm.

  As a method for dispersing the pigment, a known dispersion technique used in ink production, toner production, or the like can be used. 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, a KD mill, a colloid mill, a dynatron, a three-roll mill, and a pressure kneader. Details are described in "Latest Pigment Applied Technology" (CMC Publishing, 1986).

  When these pigments or dyes are used in combination, from the viewpoint of balance between sensitivity, layer uniformity, and durability, 0.01 to 30% by mass, preferably 0.1 to 30% by mass with respect to the total solid content constituting the recording layer. In the case of 10% by mass, particularly in the case of a dye, 0.1 to 5% by mass, and particularly in the case of a pigment, 0.2 to 10% by mass can be added.

[Water-insoluble and alkali-soluble resin]
In the recording layer according to the present invention, it is preferable to use a water-insoluble and alkali-soluble resin (hereinafter, appropriately referred to as an alkali-soluble resin) from the viewpoint of improving the film property.
Examples of the alkali-soluble resin that can be used in the positive recording layer include homopolymers containing an acidic group in the main chain and / or side chain in the polymer, copolymers thereof, or mixtures thereof.
Among them, those having the acidic groups listed in (1) to (6) mentioned in the description of the (c) acid group-containing monomer in the specific copolymer in the main chain and / or side chain of the polymer are alkaline. It is preferable in terms of solubility in a developing solution and expression of dissolution inhibiting ability.

  Among the alkali-soluble resins having an acidic group selected from the above (1) to (6), an alkali-soluble resin having (1) a phenol group, (2) a sulfonamide group, and (3) an active imide group is preferable, An alkali-soluble resin having (1) a phenol group or (2) a sulfonamide group is most preferred from the viewpoint of sufficiently ensuring solubility in an alkaline developer, development latitude, and film strength.

Hereinafter, the alkali-soluble resin having an acidic group selected from the above (1) to (6) will be described.
(1) Examples of the alkali-soluble resin having a phenol group include a condensation polymer of phenol and formaldehyde, a condensation polymer of m-cresol and formaldehyde, a condensation polymer of p-cresol and formaldehyde, m− / p. A novolak resin such as a condensation polymer of mixed cresol and formaldehyde, a condensation polymer of phenol and cresol (any of m-, p-, or m- / p-mixing) and formaldehyde, and pyrogallol and acetone Can be mentioned. Furthermore, the copolymer which copolymerized the compound which has a phenol group in a side chain can also be mentioned. Alternatively, a copolymer obtained by copolymerizing a compound having a phenol group in the side chain can also be used.

  Examples of the compound having a phenol group include acrylamide, methacrylamide, acrylic acid ester, methacrylic acid ester, and hydroxystyrene having a phenol group.

  (2) As the alkali-soluble resin having a sulfonamide group, for example, a polymer composed of a minimum constituent unit derived from a compound having a sulfonamide group as a main constituent can be mentioned. Examples of the compound as described above include compounds having at least one sulfonamide group in which at least one hydrogen atom is bonded to a nitrogen atom and one or more polymerizable unsaturated groups in the molecule. Among these, low molecular weight compounds having an acryloyl group, an allyl group, or a vinyloxy group and a substituted or monosubstituted aminosulfonyl group or a substituted sulfonylimino group in the molecule are preferable. For example, the following general formula (i) to general formula Examples include compounds represented by formula (v).

In the general formula (i) ~ formula ^{(v), X 1, X} 2 each independently represent -O- or -NR ^7. R ¹ and R ⁴ each independently represents a hydrogen atom or —CH ₃ . R ² , R ⁵ , R ⁹ , R ¹² , and R ¹⁶ each independently represent a C 1-12 alkylene group, cycloalkylene group, arylene group, or aralkylene group that may have a substituent. . R ³ , R ⁷ and R ¹³ each independently represent a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group. R ⁶ and R ¹⁷ each independently represents a C 1-12 alkyl group, cycloalkyl group, aryl group or aralkyl group which may have a substituent. 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 C 1-12 alkylene group, cycloalkylene group, arylene group or aralkylene group which may have a single bond or a substituent. Y ¹ and Y ² each independently represent a single bond or CO.

  Among the compounds represented by the general formulas (i) to (v), in the positive planographic printing plate precursor of the present invention, in particular, m-aminosulfonylphenyl methacrylate and N- (p-aminosulfonylphenyl) methacryl are used. Amide, N- (p-aminosulfonylphenyl) acrylamide and the like can be preferably used.

  (3) As an alkali-soluble resin having an active imide group, for example, a polymer composed of a minimum constituent unit derived from a compound having an active imide group as a main constituent can be mentioned. Examples of the compound as described above include compounds each having one or more active imide groups represented by the following structural formula and polymerizable unsaturated groups in the molecule.

  Specifically, N- (p-toluenesulfonyl) methacrylamide, N- (p-toluenesulfonyl) acrylamide and the like can be preferably used.

(4) As an alkali-soluble resin having a carboxylic acid group, for example, a minimum structural unit derived from a compound having at least one carboxylic acid group and polymerizable unsaturated group in the molecule is used as a main constituent component. A polymer can be mentioned.
(5) As the alkali-soluble polymer having a sulfonic acid group, for example, a minimum structural unit derived from a compound having at least one sulfonic acid group and a polymerizable unsaturated group in the molecule is a main structural unit. Can be mentioned.
(6) As an alkali-soluble resin having a phosphate group, for example, a minimum structural unit derived from a compound having at least one phosphate group and a polymerizable unsaturated group in the molecule is used as a main constituent component. A polymer can be mentioned.

  The minimum constitutional unit having an acidic group selected from the above (1) to (6) constituting the alkali-soluble resin used for the positive recording layer is not particularly limited to one kind, and is the minimum having the same acidic group. Two or more kinds of structural units or two or more kinds of minimum structural units having different acidic groups may be copolymerized.

  The copolymer preferably contains 10 mol% or more of a compound having an acidic group selected from (1) to (6) to be copolymerized, and is contained in an amount of 20 mol% or more. Those are more preferred. If it is less than 10 mol%, the development latitude tends to be insufficiently improved.

In this invention, when copolymerizing a compound and using an alkali-soluble resin as a copolymer, the other compound which does not contain the acidic group of said (1)-(6) can also be used as a compound to copolymerize. Examples of other compounds not containing an acidic group of (1) to (6) include the compounds listed in the following (m1) to (m12), but are not limited thereto.
(M1) Acrylic acid esters and methacrylic acid esters having an aliphatic hydroxyl group such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate.
(M2) Alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, benzyl acrylate, 2-chloroethyl acrylate, and glycidyl acrylate.
(M3) Alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 2-chloroethyl methacrylate, and glycidyl methacrylate.
(M4) Acrylamide, methacrylamide, N-methylol acrylamide, N-ethyl acrylamide, N-hexyl methacrylamide, N-cyclohexyl acrylamide, N-hydroxyethyl acrylamide, N-phenyl acrylamide, N-nitrophenyl acrylamide, N-ethyl- Acrylamide or methacrylamide such as N-phenylacrylamide.

(M5) 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.
(M6) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate.
(M7) Styrenes such as styrene, α-methylstyrene, methylstyrene, chloromethylstyrene.
(M8) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
(M9) Olefins such as ethylene, propylene, isobutylene, butadiene and isoprene.
(M10) N-vinylpyrrolidone, acrylonitrile, methacrylonitrile and the like.
(M11) Unsaturated imides such as maleimide, N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, N- (p-chlorobenzoyl) methacrylamide.
(M12) Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride and itaconic acid.

  The alkali-soluble resin preferably has a phenolic hydroxyl group from the viewpoint of excellent image-forming properties when exposed to infrared laser or the like. For example, a phenol formaldehyde resin, m-cresol formaldehyde resin, p-cresol formaldehyde resin, m- Preferred are novolak resins such as / p-mixed cresol formaldehyde resin and phenol / cresol (m-, p-, or m- / p-mixed) mixed formaldehyde resin and pyrogallol acetone resin.

  Further, as an alkali-soluble resin having a phenolic hydroxyl group, as described in US Pat. No. 4,123,279, a carbon number of 3 such as t-butylphenol formaldehyde resin and octylphenol formaldehyde resin is used. And a condensation polymer of phenol and formaldehyde having an alkyl group of ˜8 as a substituent.

  The alkali-soluble resin preferably has a weight average molecular weight of 500 or more from the viewpoint of image forming properties, and more preferably 1,000 to 700,000. The number average molecular weight is preferably 500 or more, and more preferably 750 to 650,000. The dispersity (weight average molecular weight / number average molecular weight) is preferably 1.1 to 10.

  These alkali-soluble resins may be used alone or in combination of two or more. In the case of combination, it has 3 to 8 carbon atoms such as a condensation polymer of t-butylphenol and formaldehyde or a condensation polymer of octylphenol and formaldehyde as described in US Pat. No. 4,123,279. A polycondensation product of phenol and formaldehyde having an alkyl group as a substituent, an alkali having a phenol structure having an electron-withdrawing group on an aromatic ring described in JP-A-2000-241972 previously filed by the present inventors A soluble resin or the like may be used in combination.

  The total content of the alkali-soluble resin in the present invention is preferably from 30 to 98% by mass, and preferably from 40 to 95% by mass in the total solid content of the recording layer, from the viewpoints of sensitivity of the recording layer, image formability and durability. % Is more preferable.

[Other additives]
(Dissolution inhibitor)
The positive recording layer according to the present invention is further thermally decomposable such as an onium salt, an o-quinonediazide compound, an aromatic sulfone compound, an aromatic sulfonic acid ester compound, and the like, and is soluble in an alkali-soluble resin when not decomposed. Can be used in combination with a substance that substantially lowers. Addition of these compounds is preferable from the viewpoint of improving dissolution inhibition of the image area in the developer.
Examples of onium salts include diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts, and arsonium salts. The onium salt is preferably added in an amount of 1 to 50% by mass, more preferably 5 to 30% by mass, and particularly preferably 10 to 30% by mass with respect to the total solid content constituting the recording layer. .

Furthermore, for the purpose of improving sensitivity, cyclic acid anhydrides, phenols, and organic acids can be used in combination.
The proportion of the cyclic acid anhydride, phenols and organic acids in the recording layer is preferably 0.05 to 20% by mass, more preferably 0.1 to 15% by mass, and particularly preferably 0.1 to 10%. % By mass.

  Besides these, epoxy compounds, vinyl ethers, further phenol compounds having a hydroxymethyl group, phenol compounds having an alkoxymethyl group described in JP-A-8-276558, and the present inventors previously proposed. A crosslinkable compound having an alkali dissolution inhibiting action described in JP-A-11-160860 can be appropriately added depending on the purpose.

  Further, in the recording layer in the present invention, a nonionic surfactant as described in JP-A-62-251740 and JP-A-3-208514 is used in order to broaden the processing stability against the development conditions. , Amphoteric surfactants as described in JP-A-59-121044 and JP-A-4-13149 can be added.

In the recording layer of the present invention, a print-out agent for obtaining a visible image immediately after heating by exposure, or a dye or pigment as an image colorant can be added.
In addition, a plasticizer is added to the recording layer of the present invention as necessary in order to impart flexibility of the coating film. For example, butylphthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, acrylic acid or methacrylic acid These oligomers and polymers are used.

[Preparation of lithographic printing plate precursor]
A lithographic printing plate precursor can be produced by dissolving the components for a coating solution of a desired layer, such as a recording layer coating solution and a protective layer coating solution according to the present invention, in a solvent and coating the solution on a suitable support. .
The recording layer may have a single layer structure or a multilayer structure.
When the recording layer of the lithographic printing plate precursor according to the present invention has a multilayer structure composed of a plurality of layers having different constituent components, for example, a lower layer containing an alkali-soluble resin, an alkali-soluble resin, and the alkali-soluble resin And an upper layer capable of forming an image by irradiation with infrared rays, and containing a specific infrared absorber in at least one of the upper layer and the lower layer Can be taken. In this case, the specific copolymer and infrared absorber in the present invention are contained in the upper layer. The lower layer may be a layer mainly composed of an alkali-soluble resin, or may further be a layer functioning as a positive recording layer containing an infrared absorber and a dissolution inhibitor.

The case where the recording layer according to the present invention has a multilayer structure will be described below.
-Lower layer component-
The lower layer according to the present invention is characterized by containing an alkali-soluble resin. As the alkali-soluble resin used here, the general alkali-soluble resin described above can be used, but in order to clarify the boundary between the upper layer and the lower layer, the alkali-soluble resin used in the lower layer is the alkali used in the upper layer. It is preferable that the main component is different from the soluble resin. Examples of the alkali-soluble resin suitably used for the lower layer include a copolymer of N- (p-aminosulfonylphenyl) (meth) acrylamide, (meth) acrylic acid alkyl ester and acrylonitrile, 4-maleimidobenzenesulfonamide and styrene. Copolymers, alkali-soluble resins having highly polar units such as copolymers of (meth) acrylic acid, N-phenylmaleimide, and (meth) acrylamide, or those resins in which the specific substituent is introduced However, the present invention is not limited to these.
The content of the total alkali-soluble resin in the lower layer of the multilayer recording layer is preferably 50 to 100% by mass in the total solid content of the lower recording layer from the viewpoint of printing durability and multilayer formation. 75 to 99% by mass, more preferably 85 to 95% by mass.
The lower layer may or may not contain the specific copolymer.

  In addition, other additives may be used for the lower layer component according to the present invention, if necessary. Examples of other additives include development accelerators, surfactants, printout / coloring agents, plasticizers, and WAX agents. Details of these components are the same as those described above.

-Upper layer component-
The upper layer according to the present invention contains an alkali-soluble resin and a compound that interacts with the alkali-soluble resin and decreases the solubility in an aqueous alkali solution (generally, an infrared-absorbing dye such as a cyanine dye having the function) An image can be formed by irradiation with infrared rays. The upper layer component is the same as that described above as the recording layer. In the present invention, the recording layer containing the specific copolymer and the infrared absorber is used as the upper layer.

Solvents used for coating the recording layer include ethylene dichloride, cyclohexanone, methyl ethyl ketone, methanol, ethanol, propanol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-methoxyethyl acetate, 1-methoxy-2. -Propyl acetate, dimethoxyethane, methyl lactate, ethyl lactate, N, N-dimethylacetamide, N, N-dimethylformamide, tetramethylurea, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, γ-butyrolactone, toluene, water, etc. However, the present invention is not limited to this. These solvents are used alone or in combination.
The concentration of the above components (total solid content including additives) in the solvent is preferably 1 to 50% by mass.

  Various methods can be used as the coating method, and examples thereof include bar coater coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating, and roll coating.

  In the recording layer coating solution according to the present invention, a surfactant for improving the coating property, for example, a fluorosurfactant described in JP-A-62-170950 may be added. it can. A preferable addition amount is 0.01 to 1% by mass in terms of solid content in the recording layer, and more preferably 0.05 to 0.5% by mass.

In the multilayer recording layer, it is preferable to form the lower layer and the upper layer by separating the two layers in principle.
As a method for forming the two layers separately, for example, a method using a difference in solvent solubility between a component contained in the lower layer and a component contained in the upper layer, or after applying the upper layer, a solvent is rapidly used. For example, a method of drying and removing.
Hereinafter, although these methods are explained in full detail, the method of isolate | separating and apply | coating two layers is not limited to these.

  As a method of utilizing the difference in solvent solubility between the component contained in the lower layer and the component contained in the upper layer, a solvent system in which any of the components contained in the lower layer is insoluble is used when the upper layer coating solution is applied. Is. Thereby, even if it carries out 2 layer application | coating, it becomes possible to isolate | separate each layer clearly and to make a coating film. For example, as the lower layer component, a component insoluble in a solvent such as methyl ethyl ketone or 1-methoxy-2-propanol that dissolves the alkali-soluble resin that is the upper layer component is selected, and the lower layer is applied using a solvent system that dissolves the lower layer component. -It is possible to form two layers by drying and then dissolving the upper layer component mainly composed of alkali-soluble resin with methyl ethyl ketone, 1-methoxy-2-propanol, etc., and applying and drying.

  Next, after applying the second layer (upper layer), as a method of drying the solvent very quickly, a method of blowing high-pressure air from a slit nozzle installed substantially perpendicular to the running direction of the web, heating with steam, etc. The method of giving thermal energy as conduction heat from the lower surface of the web from the roll (heating roll) supplied inside the medium, or a combination of these methods can be mentioned.

  Moreover, in order to provide a new function, the upper layer and the lower layer may be partially miscible in a range where the effects of the present invention are sufficiently exhibited. Such a method can be achieved by adjusting the degree of any of the above methods using the difference in solvent solubility and the method of drying the solvent very quickly after coating the second layer.

Moreover, the recording layer coating amount (solid content) on the support obtained after coating and drying varies depending on the application, but as the coating amount decreases, the apparent sensitivity increases, but the film properties of the recording layer decrease. .
In the single-layer recording layer, the coating amount of the recording layer component after drying is generally preferably from 0.5 to 5.0 g / m ² from the viewpoint of sensitivity, printing durability, and the like, and preferably from 0.7 to 4 More preferably, it is in the range of 0.0 g / m ² , more preferably in the range of 0.8 to 3.0 g / m ² .
In the multi-layer recording layer, the coating amount of the lower layer component after drying is preferably in the range of 0.5 to 4.0 g / m ² , more preferably 0.6, from the viewpoint of sensitivity and printing durability. It is in the range of ˜2.5 g / m ² . The coating amount of the upper layer component after drying is preferably in the range of 0.05 to 1.0 g / m ² , and more preferably 0.08 to 0.08 from the viewpoint of sensitivity, development latitude, scratch resistance, and the like. The range is 0.7 g / m ² .
The coating amount after drying combining the lower layer and the upper layer is preferably in the range of 0.6 to 4.0 g / m ² , more preferably from the viewpoint of sensitivity, image reproducibility, printing durability, and the like. in the range of 0.7 to 2.5 g / m ^2.

[Support]
The support used in the lithographic printing plate precursor according to the present invention is not particularly limited as long as it is a dimensionally stable plate having the required strength and durability. For example, paper, plastic (for example, Paper laminated with polyethylene, polypropylene, polystyrene, etc., metal plate (eg, aluminum, zinc, copper, etc.), plastic film (eg, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, Cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.), paper laminated with metal as described above, or vapor-deposited paper, or plastic film.

  Among them, in the present invention, a polyester film or an aluminum plate is preferable, and among them, an aluminum plate that has good dimensional stability and is relatively inexpensive is particularly preferable. A suitable aluminum plate is a pure aluminum plate or an alloy plate containing aluminum as a main component and containing a trace amount of different elements, and may be a plastic film on which aluminum is laminated or vapor-deposited. Examples of foreign elements contained in the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, and titanium. The content of foreign elements in the alloy is at most 10% by mass.

Particularly suitable aluminum in the present invention is pure aluminum, but completely pure aluminum is difficult to produce in the refining technique, and may contain slightly different elements.
Thus, the composition of the aluminum plate applied to the present invention is not specified, and an aluminum plate made of a publicly known material can be appropriately used. The thickness of the aluminum plate used in the present invention is about 0.1 mm to 0.6 mm, preferably 0.15 mm to 0.4 mm, and particularly preferably 0.2 mm to 0.3 mm.

Such an aluminum plate may be subjected to surface treatment such as roughening treatment or anodizing treatment, if necessary. Hereinafter, such a surface treatment will be briefly described.
Prior to roughening the aluminum plate, a degreasing treatment with, for example, a surfactant, an organic solvent, or an alkaline aqueous solution for removing rolling oil on the surface is performed as desired. The surface roughening treatment of the aluminum plate is performed by various methods. For example, a method of mechanically roughening, a method of electrochemically dissolving and roughening a surface, and a method of selectively dissolving a surface chemically. This is done by the method of As the mechanical method, a known method such as a ball polishing method, a brush polishing method, a blast polishing method, or a buff polishing method can be used. Further, as an electrochemical surface roughening method, there is a method of performing alternating current or direct current in hydrochloric acid or nitric acid electrolyte. Further, as disclosed in JP-A-54-63902, a method in which both are combined can also be used.
The aluminum plate roughened as described above is subjected to an alkali etching treatment and neutralization treatment as necessary, and then subjected to an anodizing treatment if desired in order to enhance the water retention and wear resistance of the surface. As the electrolyte used for the anodizing treatment of the aluminum plate, various electrolytes that form a porous oxide film can be used. In general, sulfuric acid, phosphoric acid, oxalic acid, chromic acid, or a mixed acid thereof is used. The concentration of these electrolytes is appropriately determined depending on the type of electrolyte.

The treatment conditions for anodization vary depending on the electrolyte used, and thus cannot be specified in general. In general, however, the electrolyte concentration is 1 to 80% by mass solution, the liquid temperature is 5 to 70 ° C., and the current density is 5 to 60 A / dm ^2. A voltage of 1 to 100 V and an electrolysis time of 10 seconds to 5 minutes are suitable. When the amount of the anodized film is less than 1.0 g / m ² , the printing durability is insufficient, or the non-image part of the planographic printing plate is easily damaged, and ink adheres to the damaged part during printing. So-called “scratch stains” easily occur.
After the anodizing treatment, the aluminum surface is subjected to a hydrophilic treatment if necessary.

  The hydrophilization treatment used in the present invention is disclosed in US Pat. Nos. 2,714,066, 3,181,461, 3,280,734 and 3,902,734. There are alkali metal silicate (such as aqueous sodium silicate) methods. In this method, the support is immersed in an aqueous sodium silicate solution or electrolytically treated. In addition, it is disclosed in potassium fluoride zirconate disclosed in Japanese Patent Publication No. 36-22063 and US Pat. Nos. 3,276,868, 4,153,461, and 4,689,272. A method of treating with polyvinylphosphonic acid is used.

(Undercoat layer)
In the lithographic printing plate precursor according to the invention, an undercoat layer can be provided between the support and the recording layer, if necessary.
Various organic compounds are used as the undercoat layer component. For example, phosphonic acids having an amino group such as carboxymethylcellulose, dextrin, gum arabic, 2-aminoethylphosphonic acid, phenylphosphonic acid which may have a substituent, Organic phosphonic acids such as naphthylphosphonic acid, alkylphosphonic acid, glycerophosphonic acid, methylenediphosphonic acid and ethylenediphosphonic acid, optionally substituted phenylphosphoric acid, naphthylphosphonic acid, alkylphosphoric acid and glycerophosphoric acid Organic phosphoric acid, optionally substituted phenylphosphinic acid, naphthylphosphinic acid, organic phosphinic acids such as alkylphosphinic acid and glycerophosphinic acid, amino acids such as glycine and β-alanine, and hydrochloride of triethanolamine Hydroxy groups such as Selected from hydrochloride of the amine to be, but may be used by mixing two or more.

  The undercoat layer preferably contains a compound having an onium group. The compounds having an onium group are described in detail in JP-A Nos. 2000-10292 and 2000-108538. In addition, a compound selected from the group of polymer compounds having a structural unit represented by poly (p-vinylbenzoic acid) in the molecule can also be used. Specific examples of these polymer compounds include a copolymer of p-vinylbenzoic acid and vinylbenzyltriethylammonium salt, a copolymer of p-vinylbenzoic acid and vinylbenzyltrimethylammonium chloride, and the like. .

This organic undercoat layer can be provided by the following method. That is, a method in which water or an organic solvent such as methanol, ethanol, methyl ethyl ketone, or a mixed solvent thereof is dissolved and applied on an aluminum plate and dried, and water, methanol, ethanol, methyl ethyl ketone, etc. In this method, an aluminum plate is immersed in a solution in which the above organic compound is dissolved in the above organic solvent or a mixed solvent thereof to adsorb the above compound, and then washed with water or the like and dried to provide an organic undercoat layer. In the former method, a solution having a concentration of 0.005 to 10% by mass of the organic compound can be applied by various methods. In the latter method, the concentration of the solution is 0.01 to 20% by mass, preferably 0.05 to 5% by mass, the immersion temperature is 20 to 90 ° C., preferably 25 to 50 ° C., and the immersion time is 0.1 second to 20 minutes, preferably 2 seconds to 1 minute. The solution used for this can be adjusted to a pH range of 1 to 12 with basic substances such as ammonia, triethylamine, potassium hydroxide, and acidic substances such as hydrochloric acid and phosphoric acid. A yellow dye can also be added to improve the tone reproducibility of the image recording material.
The coverage of the organic undercoat layer, from the viewpoint of printing durability, 2 to 200 mg / m ² are suitable, and preferably from 5 to 100 mg / m ^2.
The lithographic printing plate precursor produced as described above is imagewise exposed and then developed.

(Back coat layer)
A back coat layer is provided on the back surface of the support of the lithographic printing plate precursor according to the invention, if necessary. Such a back coat layer comprises a metal oxide obtained by hydrolysis and polycondensation of an organic polymer compound described in JP-A-5-45885 and an organic or inorganic metal compound described in JP-A-6-35174. A coating layer is preferably used. Among these coating layers, silicon alkoxy compounds such as Si (OCH ₃ ) ₄ , Si (OC ₂ H ₅ ) ₄ , Si (OC ₃ H ₇ ) ₄ , and Si (OC ₄ H ₉ ) ₄ are available at a low price. The coating layer of the metal oxide obtained therefrom is particularly preferable because of its excellent developer resistance.

〔exposure〕
The actinic ray light source used for image exposure of the lithographic printing plate precursor according to the invention is preferably a light source having an emission wavelength in the near infrared to infrared region, and a solid laser or a semiconductor laser is particularly preferred.

[Development processing]
The developer that can be applied to the development processing of the lithographic printing plate precursor according to the invention is a developer having a pH in the range of 9.0 to 14.0, preferably in the range of 12.0 to 13.5. A conventionally known alkaline aqueous solution can be used as the developer (hereinafter referred to as developer including the replenisher). For example, sodium silicate, potassium, tribasic sodium phosphate, potassium, ammonium, dibasic sodium phosphate, potassium, ammonium, sodium carbonate, potassium, ammonium, sodium bicarbonate, potassium, Examples include inorganic alkali salts such as ammonium, sodium borate, potassium, ammonium, sodium hydroxide, ammonium, potassium, and lithium. Moreover, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, Organic alkali agents such as ethyleneimine, ethylenediamine, and pyridine are listed. These alkaline aqueous solutions may be used individually by 1 type, and may use 2 or more types together.

  Among the above alkaline aqueous solutions, one of the developers exhibiting the effect of the present invention contains one containing an alkali silicate as a base, or an alkali silicate mixed with a silicon compound in a base, The so-called “silicate developer” is an aqueous solution having a pH of 12 or more, and another more preferable developer does not contain an alkali silicate and contains a non-reducing sugar (an organic compound having a buffering action) and a base. “Non-silicate developer”.

In the former, the aqueous solution of alkali metal silicate is a ratio of silicon oxide SiO ₂ which is a component of silicate and alkali metal oxide M ₂ O (generally expressed as a molar ratio of [SiO ₂ ] / [M ₂ O]. ) And the density, the developability can be adjusted. For example, as disclosed in JP-A-54-62004, the SiO ₂ / Na ₂ O molar ratio is 1.0 to 1.5 (that is, [SiO ₂ ] / [Na ₂ O] is 1.0 to 1.5), and an aqueous solution of sodium silicate having a SiO ₂ content of 1 to 4 mass% is disclosed in JP-B-57-7427. As described, [SiO ₂ ] / [M] is 0.5 to 0.75 (ie, [SiO ₂ ] / [M ₂ O] is 1.0 to 1.5), and SiO ₂ The developer is based on gram atoms of all alkali metals present in the developer and 1 to 4% by weight. A manner containing potassium at least 20%, aqueous solution of an alkali metal silicate is preferably used.

  A so-called “non-silicate developer” that does not contain an alkali silicate and contains a non-reducing sugar and a base is also preferable for application to the development of the lithographic printing plate precursor according to the invention. When the development processing of the lithographic printing plate precursor is performed using this developer, the surface of the recording layer is not deteriorated and the thickness of the recording layer can be maintained in a better state.

  The main component of the developer is preferably composed of at least one compound selected from non-reducing sugars and at least one base, and the pH of the solution is in the range of 9.0 to 13.5. Such non-reducing sugars are saccharides that do not have a free aldehyde group or ketone group and do not exhibit reducing properties, and are trehalose-type oligosaccharides in which reducing groups are bonded to each other, and glycosides in which a reducing group of saccharides and non-saccharides are bonded. It is classified into sugar alcohols reduced by hydrogenating the body and saccharides, and any of them is preferably used. Trehalose type oligosaccharides include saccharose and trehalose. Examples of glycosides include alkyl glycosides, phenol glycosides, mustard oil glycosides, and the like. Examples of the sugar alcohol include D, L-arabit, rebit, xylit, D, L-sorbit, D, L-mannit, D, L-exit, D, L-talit, zulsiit and allozulcit. Furthermore, maltitol obtained by hydrogenation of a disaccharide and a reduced form (reduced water candy) obtained by hydrogenation of an oligosaccharide are preferably used. Among these, sugar alcohol and saccharose are particularly preferred non-reducing sugars, and D-sorbite, saccharose, and reduced syrup are particularly preferred because they have a buffering action in an appropriate pH region and are inexpensive.

  These non-reducing sugars can be used singly or in combination of two or more, and the proportion of the non-reducing sugar in the developer is preferably 0.1 to 30% by mass from the viewpoint of buffering effect and developability, Preferably, it is 1-20 mass%.

  A conventionally known alkaline agent can be used as the base to be combined with the non-reducing sugar. For example, sodium hydroxide, potassium hydroxide, lithium hydroxide, trisodium phosphate, tripotassium phosphate, triammonium phosphate, disodium phosphate, dipotassium phosphate, diammonium phosphate, sodium carbonate, potassium carbonate, Examples include inorganic alkali agents such as ammonium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, ammonium hydrogen carbonate, sodium borate, potassium borate, and ammonium borate. Moreover, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, Organic alkali agents such as ethyleneimine, ethylenediamine, and pyridine are also used.

These alkali agents are used alone or in combination of two or more. Among these, sodium hydroxide and potassium hydroxide are preferable because the pH can be adjusted in a wide pH range by adjusting these amounts relative to the non-reducing sugar. Further, trisodium phosphate, tripotassium phosphate, sodium carbonate, potassium carbonate and the like are preferable because they have a buffering action.
These alkali agents are added so that the pH of the developer is in the range of 9.0 to 13.5, and the addition amount is determined by the desired pH, the type and addition amount of the non-reducing sugar, and more preferable pH. The range is 10.0 to 13.2.

Further, an alkaline buffer composed of a weak acid other than sugars and a strong base can be used in combination with the developer. As the weak acid used as such a buffer, one having a dissociation constant (pKa) of 10.0 to 13.2 is preferable.
Such a weak acid is selected from those described in IONATION CONSTANTS OF ORGANIC ACIDS IN AQUEOUS SOLUTION published by Pergamon Press, for example, 2,2,3,3-tetrafluoropropanol-1 (PKa12.74) , Alcohols such as trifluoroethanol (12.37) and trichloroethanol (12.24), aldehydes such as pyridine-2-aldehyde (12.68) and pyridine-4-aldehyde (12.05) , Salicylic acid (13.0), 3-hydroxy-2-naphthoic acid (12.84), catechol (12.6), gallic acid (12.4), sulfosalicylic acid (11.7) 3,4-dihydroxysulfonic acid (12) 2), 3,4-dihydroxybenzoic acid (11.94), 1,2,4-trihydroxybenzene (11.82), hydroquinone (11.56), pyrogallol (11.34), o -Compounds having phenolic hydroxyl groups such as cresol (10.33), resorcinol (11.27), p-cresol (10.27), m-cresol (10.09), 2-butanone oxime ( 12.45), acetoxime (12.42), 1,2-cycloheptanedione dioxime (12.3), 2-hydroxybenzaldehyde oxime (12.10), dimethylglyoxime (11.9) ), Ethanediamide dioxime (11.37), oximes such as acetophenone oxime (11.35), adenosine (12.5 6) Nucleic acid-related substances such as inosine (12.5), guanine (12.3), cytosine (12.2), hypoxanthine (12.1), xanthine (11.9), etc. Diethylaminomethylphosphonic acid (12.32), 1-amino-3,3,3-trifluorobenzoic acid (12.29), isopropylidenediphosphonic acid (12.10), 1,1-ethylidene Diphosphonic acid (11.54), 1,1-ethylidene diphosphonic acid 1-hydroxy (11.52), benzimidazole (12.86), thiobenzamide (12.8), picoline thioamide (same as above) Weak acids such as 12.55) and barbituric acid (12.5).

  Of these weak acids, sulfosalicylic acid and salicylic acid are preferred. As the base to be combined with these weak acids, sodium hydroxide, ammonium, potassium and lithium are preferably used. These alkali agents are used alone or in combination of two or more. The above various alkali agents are used by adjusting the pH within a preferable range by the concentration and combination.

  Various surfactants and organic solvents can be added to the developer as necessary for the purpose of promoting developability, dispersing development residue, and improving the ink affinity of the printing plate image area. Preferred surfactants include anionic, cationic, nonionic and amphoteric surfactants.

  Preferred examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene polystyryl phenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, glycerin fatty acid partial esters, sorbitan Fatty acid partial esters, pentaerythritol fatty acid partial esters, propylene glycol mono fatty acid esters, sucrose fatty acid partial esters, polyoxyethylene sorbitan fatty acid partial esters, polyoxyethylene sorbitol fatty acid partial esters, polyethylene glycol fatty acid esters, poly Glycerin fatty acid partial esters, polyoxyethylenated castor oil, polyoxyethylene glycerin fatty acid partial esters, fatty acids Nonionic surfactants such as ethanolamides, N, N-bis-2-hydroxyalkylamines, polyoxyethylene alkylamines, triethanolamine fatty acid esters, trialkylamine oxides, fatty acid salts, abietic acid salts, hydroxy Alkane sulfonates, alkane sulfonates, dialkyl sulfosuccinate esters, linear alkyl benzene sulfonates, branched alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkylphenoxy polyoxyethylene propyl sulfonates, polyoxyethylene Alkyl sulfophenyl ether salts, N-methyl-N-oleyl taurine sodium salt, N-alkyl sulfosuccinic acid monoamide disodium salt, petroleum sulfonates, sulfated tallow oil Fatty acid alkyl ester sulfate ester salt, alkyl sulfate ester salt, polyoxyethylene alkyl ether sulfate ester salt, fatty acid monoglyceride sulfate ester salt, polyoxyethylene alkylphenyl ether sulfate ester salt, polyoxyethylene styryl phenyl ether sulfate ester salt, alkyl phosphorus Acid ester salts, polyoxyethylene alkyl ether phosphoric acid ester salts, polyoxyethylene alkyl phenyl ether phosphoric acid ester salts, partially saponified products of styrene / leic anhydride copolymer, partial saponification of olefin / maleic anhydride copolymer Products, anionic surfactants such as naphthalenesulfonate formalin condensates, alkylamine salts, quaternary ammonium salts such as tetrabutylammonium bromide, Examples include cationic surfactants such as reoxyethylene alkylamine salts and polyethylene polyamine derivatives, and amphoteric surfactants such as carboxybetaines, aminocarboxylic acids, sulfobetaines, aminosulfuric esters, and imidazolines. Among the surfactants listed above, those having polyoxyethylene can be read as polyoxyalkylenes such as polyoxymethylene, polyoxypropylene and polyoxybutylene, and these surfactants are also included.

  A more preferred surfactant is a fluorosurfactant containing a perfluoroalkyl group in the molecule. Such fluorosurfactants include perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, anionic types such as perfluoroalkyl phosphates, amphoteric types such as perfluoroalkyl betaines, and perfluoroalkyltrimethylammonium salts. Cationic and perfluoroalkyl amine oxides, perfluoroalkyl ethylene oxide adducts, perfluoroalkyl group and hydrophilic group-containing oligomers, perfluoroalkyl group and lipophilic group-containing oligomers, perfluoroalkyl groups, hydrophilic groups and lipophilic groups Nonionic types such as group-containing oligomers, perfluoroalkyl groups, and lipophilic group-containing urethanes can be mentioned. Said surfactant can be used individually or in combination of 2 or more types, and is added in 0.001-10 mass% in a developing solution, More preferably, it is added in 0.01-5 mass%.

  Various development stabilizers can be used in the developer. Preferred examples thereof include polyethylene glycol adducts of sugar alcohols described in JP-A-6-282079, tetraalkylammonium salts such as tetrabutylammonium hydroxide, phosphonium salts such as tetrabutylphosphonium bromide, and iodonium such as diphenyliodonium chloride. A salt is a preferred example. Furthermore, anionic surfactants or amphoteric surfactants described in JP-A-50-51324, water-soluble cationic polymers described in JP-A-55-95946, and JP-A-56-142528 are described. And water-soluble amphoteric polymer electrolytes that have been used.

  Furthermore, an organic boron compound to which an alkylene glycol is added as described in JP-A-59-84241, a polyoxyethylene / polyoxypropylene block polymerization type water-soluble surfactant as described in JP-A-60-111246, An alkylenediamine compound substituted with polyoxyethylene / polyoxypropylene disclosed in JP-A-60-129750, a polyethylene glycol having a weight average molecular weight of 300 or more described in JP-A-61-215554, and a cation described in JP-A-63-175858 And a fluorine-containing surfactant having a functional group, a water-soluble ethylene oxide addition compound obtained by adding 4 mol or more of ethylene oxide to an acid or alcohol disclosed in JP-A-2-39157, and a water-soluble polyalkylene compound.

If necessary, an organic solvent is further added to the developer. As such an organic solvent, those having a solubility in water of about 10% by mass or less are suitable, and are preferably selected from those having 5% by mass or less. For example, 1-phenylethanol, 2-phenylethanol, 3-phenyl-1-propanol, 4-phenyl-1-butanol, 4-phenyl-2-butanol, 2-phenyl-1-butanol, 2-phenoxyethanol, 2- Benzyloxyethanol, o-methoxybenzyl alcohol, m-methoxybenzyl alcohol, p-methoxybenzyl alcohol, benzyl alcohol, cyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol and 4-methylcyclohexanol, N-phenylethanol Examples include amines and N-phenyldiethanolamine.
Content of the organic solvent is 0.1-5 mass% with respect to the total mass of a use liquid. The amount used is closely related to the amount of surfactant used, and it is preferable to increase the amount of surfactant as the amount of organic solvent increases. This is because the amount of the surfactant is small, and when the amount of the organic solvent is large, the organic solvent is not completely dissolved, so that it is impossible to expect good developability.

A reducing agent can be further added to the developer. This prevents the printing plate from being stained. Preferable organic reducing agents include phenol compounds such as thiosalicylic acid, hydroquinone, metol, methoxyquinone, resorcin, and 2-methylresorcin, and amine compounds such as phenylenediamine and phenylhydrazine. More preferable inorganic reducing agents include sodium, potassium and ammonium salts of inorganic acids such as sulfurous acid, bisulfite, phosphorous acid, hydrogen phosphite, dihydrogen phosphite, thiosulfuric acid and dithionite. A salt etc. can be mentioned.
Among these reducing agents, sulfites are particularly excellent in the antifouling effect. These reducing agents are preferably contained in the range of 0.05 to 5% by mass with respect to the developer at the time of use.

  An organic carboxylic acid can also be added to the developer. Preferred organic carboxylic acids are aliphatic carboxylic acids and aromatic carboxylic acids having 6 to 20 carbon atoms. Specific examples of the aliphatic carboxylic acid include caproic acid, enanthylic acid, caprylic acid, lauric acid, myristic acid, palmitic acid and stearic acid, and particularly preferred are alkanoic acids having 8 to 12 carbon atoms. . Further, it may be an unsaturated fatty acid having a double bond in the carbon chain or a branched carbon chain. The aromatic carboxylic acid is a compound in which a carboxyl group is substituted on a benzene ring, naphthalene ring, anthracene ring or the like, and specifically includes o-chlorobenzoic acid, p-chlorobenzoic acid, o-hydroxybenzoic acid, p- Hydroxybenzoic acid, o-aminobenzoic acid, p-aminobenzoic acid, 2,4-dihydrobenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 3, There are 5-dihydroxybenzoic acid, gallic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 2-hydroxy-1-naphthoic acid, 1-naphthoic acid, 2-naphthoic acid and the like. Naphthoic acid is particularly effective.

  The aliphatic and aromatic carboxylic acids are preferably used as sodium salts, potassium salts or ammonium salts in order to enhance water solubility. The content of the organic carboxylic acid in the developer used in the present invention is not particularly limited, but if it is less than 0.1% by mass, the effect is not sufficient, and if it is 10% by mass or more, the effect cannot be further improved. In addition, dissolution may be hindered when other additives are used in combination. Therefore, the preferable addition amount is 0.1 to 10% by mass, and more preferably 0.5 to 4% by mass with respect to the developing solution at the time of use.

  If necessary, the developer may further contain a preservative, a colorant, a thickener, an antifoaming agent, a hard water softening agent, and the like. Examples of water softeners include polyphosphoric acid and its sodium, potassium and ammonium salts, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, hydroxyethylethylenediaminetriacetic acid, nitrilotriacetic acid, 1,2-diaminocyclohexanetetra Aminopolycarboxylic acids such as acetic acid and 1,3-diamino-2-propanoltetraacetic acid and their sodium, potassium and ammonium salts, aminotri (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylene Phosphonic acid), triethylenetetramine hexa (methylenephosphonic acid), hydroxyethylethylenediaminetri (methylenephosphonic acid) and 1-hydro The lower edge 1,1-diphosphonic acid and their sodium salts, potassium salts and ammonium salts.

  The optimum value of such a hard water softener varies depending on its chelation and the hardness of the hard water used and the amount of hard water. %, More preferably in the range of 0.01 to 0.5 mass%. If the addition amount is less than this range, the intended purpose is not sufficiently achieved. If the addition amount is more than this range, adverse effects on the image area such as color loss will occur. The remaining component of the developer is water. It is advantageous in terms of transportation that the developer is a concentrated solution having a water content less than that in use and is diluted with water when in use. In this case, the degree of concentration is appropriate such that each component does not cause separation or precipitation.

The developer described in JP-A-6-282079 can also be used as the developer used in the present invention. This is because 5 mol or more of ethylene oxide is added to an alkali metal silicate having a molar ratio of SiO ₂ / M ₂ O (M represents an alkali metal) of 0.5 to 2.0 and a sugar alcohol having 4 or more hydroxyl groups. A developer containing a water-soluble ethylene oxide addition compound obtained in this manner. Sugar alcohols are polyhydric alcohols corresponding to those obtained by reducing aldehyde groups and ketone groups of sugars to form primary and secondary alcohol groups, respectively. Examples of sugar alcohol shells include D, L-trait, erythritol, D, L-arabit, rebit, xylit, D, L-sorbit, D, L-mannit, D, L-exit, D, Examples thereof include L-talit, dulcit, and allozulcit, and di-, tri-, tetra-, penta-, and hexaglycerin condensed with a sugar alcohol. The water-soluble ethylene oxide addition compound can be obtained by adding 5 mol or more of ethylene oxide to 1 mol of the sugar alcohol. Further, propylene oxide may be block-copolymerized to the ethylene oxide addition compound as required within a range where solubility is acceptable. These ethylene oxide addition compounds may be used alone or in combination of two or more.
The addition amount of these water-soluble ethylene oxide addition compounds is suitably 0.001 to 5% by mass, more preferably 0.001 to 2% by mass, with respect to the developer (use solution).

  The developer may further contain the above-described various surfactants and organic solvents as needed for the purpose of promoting developability, dispersing development residue, and improving ink affinity of the printing plate image area.

  A lithographic printing plate precursor developed with a developer having such a composition is subjected to post-treatment with a washing water, a rinse solution containing a surfactant, a finisher mainly composed of gum arabic or starch derivatives, or a protective gum solution. The These treatments can be used in various combinations for the post-treatment of the lithographic printing plate precursor according to the invention.

  In recent years, automatic developing machines for PS plates have been widely used in the stencil and printing industries in order to rationalize and standardize plate making operations. This automatic developing machine is generally composed of a developing unit and a post-processing unit, and includes an apparatus for conveying the PS plate, each processing liquid tank and a spray device, and the exposed PS plate is pumped up while being transported horizontally. Each processing solution is sprayed from a spray nozzle to develop and post-process. In addition, recently, a PS plate is immersed and transported in a processing solution tank filled with a processing solution by a guide roll in the solution, and a small amount of washing water after development is supplied to the plate surface for washing. A method is also known in which the waste water is reused as dilution water for the developer stock solution.

  In such automatic processing, each processing solution can be processed while being replenished with each replenisher according to the processing amount, operating time, and the like. In addition, a so-called disposable processing method in which processing is performed with a substantially unused processing solution can also be applied.

  In the lithographic printing plate precursor according to the invention, image portions unnecessary for the lithographic printing plate obtained by image exposure, development, washing and / or rinsing and / or gumming (for example, film edge marks of the original film, etc.) ), Unnecessary image portions are erased. Such erasing is preferably performed by applying an erasing solution as described in, for example, Japanese Patent Publication No. 2-13293 to an unnecessary image portion, leaving it for a predetermined time, and then washing with water. As described in JP-A-59-174842, a method of developing after irradiating an unnecessary image portion with an actinic ray guided by an optical fiber can also be used.

The lithographic printing plate obtained from the lithographic printing plate precursor of the present invention as described above can be subjected to a printing process after applying a desensitizing gum if desired, but lithographic printing with a higher printing durability. If you want to make a plate, you will be burned. In the case of burning a lithographic printing plate, before burning, an adjustment as described in JP-B-61-2518, JP-A-55-28062, JP-A-62-31859, JP-A-61-159655 is used. It is preferable to treat with a surface liquid.
As its method, with a sponge or absorbent cotton soaked with the surface-adjusting liquid, it is applied onto a lithographic printing plate, or a method in which the printing plate is immersed and applied in a vat filled with the surface-adjusting liquid, Application by an automatic coater is applied. Further, it is more preferable to make the coating amount uniform with a squeegee or a squeegee roller after coating.

In general, the amount of surface-adjusting solution applied is suitably 0.03 to 0.8 g / m ² (dry mass). The lithographic printing plate coated with the surface-adjusting liquid is dried if necessary, and then heated to a high temperature with a burning processor (for example, burning processor “BP-1300” sold by Fuji Photo Film Co., Ltd.). Is done. In this case, the heating temperature and time are in the range of 180 to 300 ° C. and preferably in the range of 1 to 20 minutes, although depending on the type of components forming the image.

  The lithographic printing plate that has been burned can be subjected to conventional treatments such as washing and gumming as needed, but a surface-conditioning solution containing a water-soluble polymer compound is used. In such a case, a so-called desensitizing treatment such as gumming can be omitted. The planographic printing plate obtained by such processing is applied to an offset printing machine or the like and used for printing a large number of sheets.

  EXAMPLES Hereinafter, although this invention is demonstrated according to an Example, the scope of the present invention is not limited to these Examples.

(Production of support)
Supports A, B, C, and D were prepared by using a JIS-A-1050 aluminum plate having a thickness of 0.3 mm in combination with the following processes.

(A) Mechanical surface roughening treatment While supplying a suspension of abrasive (silica sand) having a specific gravity of 1.12 and water as a polishing slurry liquid to a surface of an aluminum plate, it is mechanically rotated by a roller-like nylon brush. Roughening was performed. The average particle size of the abrasive was 8 μm, and the maximum particle size was 50 μm. The material of the nylon brush was 6 · 10 nylon, the hair length was 50 mm, and the hair diameter was 0.3 mm. The nylon brush was planted so as to be dense by making a hole in a stainless steel tube having a diameter of 300 mm. Three rotating brushes were used. The distance between the two support rollers (φ200 mm) at the bottom of the brush was 300 mm. The brush roller was pressed until the load of the drive motor for rotating the brush became 7 kW plus with respect to the load before the brush roller was pressed against the aluminum plate. The rotating direction of the brush was the same as the moving direction of the aluminum plate. The rotation speed of the brush was 200 rpm.

(B) Alkali etching treatment The aluminum plate obtained above was sprayed with an aqueous NaOH solution at a temperature of 70 ° C. (concentration 26 mass%, aluminum ion concentration 6.5 mass%) to carry out an etching treatment. ² dissolved. Thereafter, washing with water was performed using well water.

(C) Desmutting treatment Desmutting treatment was performed by spraying with a 1% by weight aqueous solution of nitric acid at a temperature of 30 ° C. (containing 0.5% by weight of aluminum ions), and then washed with water by spraying. The nitric acid aqueous solution used for the desmut was the waste liquid from the step of electrochemical surface roughening using alternating current in nitric acid aqueous solution.

(D) Electrochemical roughening treatment An electrochemical roughening treatment was carried out continuously using an alternating voltage of 60 Hz. The electrolytic solution at this time was a nitric acid 10.5 g / liter aqueous solution (aluminum ion 5 g / liter) at a temperature of 50 ° C. The AC power supply waveform has an electrochemical surface roughening treatment using a carbon electrode as a counter electrode using a trapezoidal rectangular wave alternating current with a time TP of 0.8 msec until the current value reaches a peak from zero, a DUTY ratio of 1: 1. went. Ferrite was used for the auxiliary anode. The electrolytic cell used was a radial cell type.
The current density was 30 A / dm ² at the peak current value, and the amount of electricity was 220 C / dm ² in terms of the total amount of electricity when the aluminum plate was the anode. 5% of the current flowing from the power source was shunted to the auxiliary anode.
Thereafter, washing with water was performed using well water.

(E) Alkali etching treatment The aluminum plate was sprayed at a caustic soda concentration of 26% by mass and an aluminum ion concentration of 6.5% by mass at 32 ° C. to dissolve the aluminum plate by 0.20 g / m ² , The smut component mainly composed of aluminum hydroxide generated when electrochemical surface roughening was used was removed, and the edge portion of the generated pit was melted to smooth the edge portion. Thereafter, washing with water was performed using well water.

(F) Desmut treatment Desmut treatment by spraying was performed with a 15% by weight aqueous solution of nitric acid at a temperature of 30 ° C. (including 4.5% by weight of aluminum ions), and then washed with water using well water. The nitric acid aqueous solution used for the desmut was the waste liquid from the step of electrochemical surface roughening using alternating current in nitric acid aqueous solution.

(G) Electrochemical surface roughening treatment An electrochemical surface roughening treatment was performed continuously using an alternating voltage of 60 Hz. The electrolytic solution at this time was a hydrochloric acid 7.5 g / liter aqueous solution (containing 5 g / liter of aluminum ions) at a temperature of 35 ° C. The AC power supply waveform was a rectangular wave, and an electrochemical surface roughening treatment was performed using a carbon electrode as a counter electrode. Ferrite was used for the auxiliary anode. The electrolytic cell used was a radial cell type.
The current density was 25 A / dm ² at the peak current value, and the amount of electricity was 50 C / dm ² in terms of the total amount of electricity when the aluminum plate was the anode.
Thereafter, washing with water was performed using well water.

(H) Alkaline etching treatment An aluminum plate is etched by spraying at 32 ° C. with a caustic soda concentration of 26% by mass and an aluminum ion concentration of 6.5% by mass, and the aluminum plate is dissolved at 0.10 g / m ² , so The smut component mainly composed of aluminum hydroxide generated during the electrochemical surface roughening treatment was removed, and the edge portion of the generated pit was melted to smooth the edge portion. Thereafter, washing with water was performed using well water.

(I) Desmut treatment A desmut treatment by spraying was performed with a 25% by mass aqueous solution of sulfuric acid at a temperature of 60 ° C. (containing 0.5% by mass of aluminum ions), and then water washing by spraying was performed using well water.

(J) Anodizing treatment As the electrolytic solution, sulfuric acid was used. All electrolytes had a sulfuric acid concentration of 170 g / liter (containing 0.5 mass% of aluminum ions), and the temperature was 43 ° C. Thereafter, washing with water was performed using well water.
Both current densities were about 30 A / dm ² . The final oxide film amount was 2.7 g / m ² .

<Support A>
The steps (a) to (j) were performed in order, and the support was prepared so that the etching amount in the step (e) was 3.4 g / m ² .

<Support B>
Except for omitting the steps (g), (h) and (i) among the above steps, each step was performed in order to prepare a support.

<Support C>
A support was prepared by sequentially performing each step except that the steps (a), (g), (h), and (i) were omitted.

<Support D>
Except for omitting the process of the above step (a) and (d) (e) (f ) performs the steps in turn, supported as total amount of electricity is 450C / dm ² in step (g) The body was made.

  Supports A, B, C, and D obtained as described above were subsequently subjected to the following hydrophilization treatment and undercoating treatment.

(K) Alkali metal silicate treatment Alkali metal silicate is obtained by immersing the aluminum support obtained by the anodizing treatment in a treatment layer of No. 3 sodium silicate 1 mass% aqueous solution at a temperature of 30 ° C. for 10 seconds. Salt treatment (silicate treatment) was performed. Then, the water washing by the spray using well water was performed. The amount of silicate adhering at that time was 3.6 mg / m ² .

(Undercoating)
On the aluminum support after the alkali metal silicate treatment obtained as described above, an undercoat solution having the following composition was applied and dried at 80 ° C. for 15 seconds. The coating amount after drying was 16 mg / m ² .

<Undercoat liquid composition>
・ The following polymer compound 0.3g
・ Methanol 100g
・ Water 1.0g

[ Reference Examples 1-4, 9, 10, Examples 5-8, Comparative Examples 1-4]
A coating solution for the first layer (lower layer) having the following composition was applied to the obtained support A with a wire bar, and then dried in a drying oven at 150 ° C. for 60 seconds to obtain a coating amount of 0.85 g / m ² . did.
A coating solution for the second layer (upper layer) having the following composition was applied to the obtained support with a lower layer with a wire bar. After coating, drying is performed in a drying oven at 145 ° C. for 70 seconds, and the total coating amount is set to 1.15 g / m ^2. Reference Examples 1 to 4 , 9, 10, Examples 5 to 8 and Comparative Examples 1 to 4 A positive lithographic printing plate precursor was prepared.

<First layer (lower layer) coating solution>
-Copolymer 1 (synthesized by the following) 2.133 g
・ Cyanine dye A (the following structure) 0.098g
2-Mercapto-5-methylthio-1,3,4-thiadiazole
0.030g
・ Cis-Δ ⁴ -tetrahydrophthalic anhydride 0.100 g
・ 4,4'-sulfonyldiphenol 0.090g
・ 0.008 g of p-toluenesulfonic acid
-The counter anion of ethyl violet is changed to 6-hydroxynaphthalenesulfonic acid 0.100 g
・ 3-Methoxy-4-diazodiphenylamine hexafluorophosphate
0.030g
・ Fluorosurfactant 0.035g
(Megafuck F-780, manufactured by Dainippon Ink & Chemicals, Inc.)
・ Methyl ethyl ketone 26.6g
1-methoxy-2-propanol 13.6 g
・ Γ-Butyrolactone 13.8g

<Synthesis of Copolymer 1>
After stirring, 31.0 g (0.36 mol) of methacrylic acid, 39.1 g (0.36 mol) of ethyl chloroformate and 200 ml of acetonitrile were placed in a 500 ml three-necked flask equipped with a condenser and a dropping funnel, and cooled in an ice-water bath. The mixture was stirred while. To this mixture, 36.4 g (0.36 mol) of triethylamine was dropped with a dropping funnel over about 1 hour. After completion of the dropwise addition, the ice-water bath was removed, and the mixture was stirred at room temperature for 30 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, the mixture was added to 1 liter of water with stirring, and the resulting mixture was stirred for 30 minutes. The mixture was filtered to take out a precipitate, which was slurried with 500 ml of water, then the slurry was filtered, and the obtained solid was dried to dry a white solid of N- (p-aminosulfonylphenyl) methacrylamide. Was obtained (yield 46.9 g).

  Next, 4.61 g (0.0192 mol) of N- (p-aminosulfonylphenyl) methacrylamide and 2.58 g of ethyl methacrylate (0.0258 mol) were added to a 20 ml three-necked flask equipped with a stirrer, a condenser and a dropping funnel. ), 0.80 g (0.015 mol) of acrylonitrile and 20 g of N, N-dimethylacetamide were added, and the mixture was stirred while heating to 65 ° C. with a hot water bath. To this mixture, 0.15 g of 2,2′-azobis (2,4-dimethylvaleronitrile) (trade name: “V-65”, manufactured by Wako Pure Chemical Industries, Ltd.) was added as a polymerization initiator and maintained at 65 ° C. The mixture was stirred for 2 hours under a nitrogen stream. This reaction mixture was further mixed with 4.61 g of N- (p-aminosulfonylphenyl) methacrylamide, 2.58 g of methyl methacrylate, 0.80 g of acrylonitrile, 20 g of N, N-dimethylacetamide and 0.15 g of “V-65”. Was dropped by a dropping funnel over 2 hours. After completion of the dropwise addition, the resulting mixture was further stirred at 65 ° C. for 2 hours. After completion of the reaction, 40 g of methanol was added to the mixture, cooled, and the resulting mixture was poured into 2 liters of water while stirring the water. After stirring the mixture for 30 minutes, the precipitate was removed by filtration and dried. 15 g of a white solid was obtained. It was 54,000 when the weight average molecular weight (polystyrene standard) of this specific copolymer 1 was measured by the gel permeation chromatography.

<Second layer (upper layer) coating solution>
Copolymer of ethyl methacrylate and 2-methacryloyloxyethyl succinic acid (molar ratio 67:33, weight average molecular weight 92,000) 0.030 g
Novolak resin P1: phenol cresol-formaldehyde novolak (phenol: m-cresol: p-cresol = 30: 30: 40, weight average molecular weight: 5500) 0.300 g
・ Sulphonium salt (the following structure) 0.1g
・ Cyanine dye A (the above structure) 0.015 g
-Ethyl violet counter anion changed to 6-hydroxynaphthalenesulfonic acid 0.012 g
・ Fluorine-based surfactant 0.011g
(Megafuck F-780, manufactured by Dainippon Ink & Chemicals, Inc.)
・ Methyl ethyl ketone 13.1g
1-methoxy-2-propanol 6.79g
Specific copolymer or comparative copolymer (compound described in Table 1) 0.055 g

  Moreover, the structure of the comparative example copolymer used for each comparative example is shown below with the weight average molecular weight (Mw).

[Evaluation of lithographic printing plate precursor]
The evaluation of the lithographic printing plate precursor was conducted for each of the development latitude, sensitivity, and shrinkability. Details of the evaluation method are as follows.

1. Existence of sludge generation After blasting the whole surface of the lithographic printing plate precursor 1 m ² , a developer (DT-1) 100 cc made by Fuji Photo Film Co., Ltd., which is a developer containing substantially no alkali metal silicate Then, it was evaluated whether sludge due to precipitates and aggregates derived from the specific copolymer according to the present invention was generated in the processing solution. The case where generation | occurrence | production was not able to be confirmed visually was evaluated as (circle), and the case where generation | occurrence | production of sludge by deposit and an aggregate was confirmed visually was evaluated as x. The results are shown in Table 1 below.
2. Attaching property The lithographic printing plate precursor is imagewise exposed using a TrendSetter 3244F manufactured by CREO with a setter exposure of 8.0 W and 150 rpm, and a developer DT-1 for PS plate manufactured by Fuji Photo Film Co., Ltd. is used as a standard. After developing using the conditions, it was applied to a printing machine, and the number of printed sheets required to obtain a printed matter having no problem on the image area was evaluated. The smaller the number, the better the inking property. The results are listed in Table 1 below.

As shown in Table 1, it can be seen that the lithographic printing plate precursors of Examples 5 to 8 achieve improvement in the inking property. In addition, generation of sludge due to precipitates in the developer was not observed. On the other hand, all of the lithographic printing plate precursors of Comparative Examples 1 to 4 were inferior in thickness to the examples, and generation of sludge due to precipitates in the developer was observed.

[ Reference Examples 11, 16, 17, Examples 12-15 , 18-20 , Comparative Examples 5-8]
Reference Examples 11, 16, 17, Examples 12-15, 18-20, and Comparative Examples 5-8 are the second of Reference Examples 1-4, 9, 10, Examples 5-8, and Comparative Examples 1-4. Evaluations were all made in the same manner except that the sulfonium salt was removed from the layer (upper layer) coating solution and the copolymer was changed to the compounds shown in Table 2. The results are shown in Table 2.

As shown in Table 2, it can be seen that the lithographic printing plate precursors of Examples 12 to 15 and 18 to 20 achieve improvement in the inking property and the generation of sludge is suppressed. On the other hand, all of the lithographic printing plate precursors of Comparative Examples 5 to 8 that do not contain the specific copolymer according to the present invention are inferior in thickness to the examples and are caused by precipitates in the developer. Occurrence of sludge was observed. Further, it can be seen from this result that the effects of the present invention can be obtained regardless of the presence or absence of the sulfonium salt in the recording layer.

[ Reference Examples 21 and 25, Examples 22 to 24 , 25 to 28, Comparative Examples 9 to 10]
A coating solution for the first layer (lower layer) having the following composition was applied to the obtained support C with a wire bar, and then dried in a drying oven at 130 ° C. for 60 seconds to obtain a coating amount of 0.60 g / m ² . did.
A coating solution for the second layer (upper layer) having the following composition was applied to the obtained support with a lower layer with a wire bar. After coating, drying is performed at 150 ° C. for 60 seconds in a drying oven, and the total coating amount is set to 1.25 g / m ² , and Reference Examples 21 and 25, Examples 22 to 24 , 25 to 28, and Comparative Examples 9 to 10 are performed. Positive type lithographic printing plate precursors of Examples 21 to 28 and Comparative Examples 9 to 10 were prepared.

<First layer (lower layer) coating solution>
・ Copolymer 1 2.133 g
・ Cyanine dye A (the above structure) 0.098 g
2-Mercapto-5-methylthio-1,3,4-thiadiazole
0.030g
・ Cis-Δ ⁴ -tetrahydrophthalic anhydride 0.100 g
・ 4,4'-sulfonyldiphenol 0.090g
・ 0.008 g of p-toluenesulfonic acid
-The counter anion of ethyl violet is changed to 6-hydroxynaphthalenesulfonic acid 0.100 g
・ 3-Methoxy-4-diazodiphenylamine hexafluorophosphate
0.030g
・ Fluorosurfactant 0.035g
(Megafuck F-780, manufactured by Dainippon Ink & Chemicals, Inc.)
・ Methyl ethyl ketone 26.6g
1-methoxy-2-propanol 13.6 g
・ Dimethylsulfoxide 13.8g

<Second layer (upper layer) coating solution>
Copolymer of ethyl methacrylate and 2-methacryloyloxyethyl succinic acid (molar ratio 67:33, weight average molecular weight 92,000) 0.030 g
Novolak resin P1: phenol cresol-formaldehyde novolak (phenol: m-cresol: p-cresol = 30: 30: 40, weight average molecular weight: 5500) 0.300 g
・ Sulphonium salt (the above structure) 0.1g
・ Cyanine dye A (the above structure) 0.015 g
-Ethyl violet counter anion changed to 6-hydroxynaphthalenesulfonic acid 0.012 g
・ Fluorine-based surfactant 0.011g
(Megafuck F-780, manufactured by Dainippon Ink & Chemicals, Inc.)
・ Methyl ethyl ketone 13.1g
1-methoxy-2-propanol 6.79g
-Specific copolymer or comparative copolymer (compound described in Table 3) 0.055 g

<Evaluation of Reference Examples 21 and 25, Examples 22 to 28 and Comparative Examples 9 to 10>
The obtained lithographic printing plate precursors of Reference Examples 21 and 25, Examples 22 to 24, 26 to 28, and Comparative Examples 9 to 10 were evaluated in the same manner as in Example 1.

As shown in Table 3, the lithographic printing plate precursors of Examples 22 to 24 and 26 to 28 achieved improvement in the wall- thickness property and no generation of sludge due to precipitates in the developer. I understand that. On the other hand, the lithographic printing plate precursors of Comparative Examples 9 to 10 which do not contain the specific copolymer according to the present invention in the recording layer are all inferior in thickness to the examples, and precipitates in the developer Occurrence of sludge caused by the

[ Reference Examples 29-31, Examples 32-36, Comparative Examples 11-12]
Reference Examples 29 to 31, Examples 32 to 36 and Comparative Examples 11 to 12 were obtained by applying a sulfonium salt from the coating solution for the second layer (upper layer) of Reference Examples 21 and 25, Examples 22 to 28 and Comparative Examples 9 to 10. Except that the copolymer was replaced with the compounds listed in Table 4, all were evaluated in the same manner. The results are shown in Table 4.

As shown in Table 4, it can be seen that the lithographic printing plate precursors of Examples 32 to 36 achieve an improvement in the inking property, and there is no generation of sludge due to precipitates in the developer. On the other hand, the planographic printing plate precursors of Comparative Examples 11 to 12 which do not contain the specific copolymer according to the present invention in the recording layer are all inferior in thickness to the examples, and precipitates in the developer Occurrence of sludge caused by the

[ Reference Examples 37, 38, 43, 44, Examples 39 to 42 , Comparative Examples 13 to 14]
A coating solution for the first layer (lower layer) having the following composition was applied to the obtained support D with a wire bar, and then dried in a drying oven at 150 ° C. for 60 seconds to obtain a coating amount of 0.81 g / m ² . did.
A coating solution for the second layer (upper layer) having the following composition was applied to the obtained support with a lower layer with a wire bar. After coating, drying was performed in a drying oven at 150 ° C. for 60 seconds, and the total coating amount was set to 0.99 g / m ² , and Reference Examples 37, 38, 43, 44, Examples 39 to 42 and Comparative Examples 13 to 14 A positive lithographic printing plate precursor was prepared.

<First layer (lower layer) coating solution>
-Copolymer 1 2.133 g
・ Cyanine dye A (the above structure) 0.098 g
・ Cis-Δ ⁴ -tetrahydrophthalic anhydride 0.110 g
・ 4,4'-sulfonyldiphenol 0.090g
・ 0.008 g of p-toluenesulfonic acid
-The counter anion of ethyl violet is changed to 6-hydroxynaphthalenesulfonic acid 0.100 g
・ 3-Methoxy-4-diazodiphenylamine hexafluorophosphate
0.030g
・ Fluorosurfactant 0.035g
(Megafuck F-780, manufactured by Dainippon Ink & Chemicals, Inc.)
・ Methyl ethyl ketone 26.6g
1-methoxy-2-propanol 13.6 g
・ Γ-Butyrolactone 13.8g

<Second layer (upper layer) coating solution>
Copolymer of ethyl methacrylate and 2-methacryloyloxyethyl succinic acid (molar ratio 67:33, weight average molecular weight 92,000) 0.030 g
Novolak resin P5: phenol cresol-formaldehyde novolak (phenol: m-cresol: p-cresol = 40: 40: 20, weight average molecular weight: 8000) 0.300 g
・ Sulphonium salt (the above structure) 0.020 g
・ Cyanine dye A (the above structure) 0.015 g
・ Fluorine-based surfactant 0.011g
(Megafuck F-780, manufactured by Dainippon Ink & Chemicals, Inc.)
・ Methyl ethyl ketone 13.1g
1-methoxy-2-propanol 6.79g
-Specific copolymer or comparative copolymer (compound described in Table 5) 0.055 g

< Evaluation of Reference Examples 37, 38, 43, 44, Examples 39 to 42 and Comparative Examples 13 to 14>
The obtained lithographic printing plate precursor was used in Example 1 except that a developer (DP-4) of a developer (produced by Fuji Photo Film Co., Ltd.) containing an alkali metal silicate was used as the developer. Evaluation was performed in the same manner.

As shown in Table 5, it can be seen that the lithographic printing plate precursors of Examples 39 to 42 achieve an improvement in the inking property, and there is no generation of sludge due to precipitates in the developer. On the other hand, the lithographic printing plate precursors of Comparative Examples 13 to 14 which do not contain the specific copolymer according to the present invention in the recording layer are all inferior in thickness to the examples, and precipitates in the developer. Occurrence of sludge caused by the

[ Reference Examples 45, 48, 50, Examples 46, 47, 49, 51 to 52, Comparative Examples 15 to 16]
In Reference Examples 45, 48, 50, Examples 46, 47, 49, 51 and Comparative Examples 15 to 16, the sulfonium salt was obtained from the coating solution for the second layer (upper layer) of Examples 37 to 44 and Comparative Examples 13 to 14. Except that the copolymer was changed to the compounds shown in Table 6, all were evaluated in the same manner. The results are shown in Table 6.

  As shown in Table 6, it can be seen that the lithographic printing plate precursors of Examples 45 to 52 achieved improvement in the wall thickness and no generation of sludge due to precipitates in the developer. On the other hand, all of the lithographic printing plate precursors of Comparative Examples 15 to 16 that do not contain the specific copolymer according to the present invention are inferior in thickness as compared with Examples, and are caused by precipitates in the developer. Occurrence of sludge was observed.

[ Reference Examples 53 and 54, Examples 55 to 60, Comparative Examples 17 to 18]
The following image forming layer coating solution was applied to the obtained support D and dried at 150 ° C. for 1 minute to form an image forming layer. The planographic printing of Examples 53 to 60 and Comparative Examples 17 to 18 I got the original version. The coating amount after drying was 1.55 g / m ² .

<Image forming layer coating solution>
Novolak resin P7: phenol cresol-formaldehyde novolak (phenol: m-cresol: p-cresol = 20: 60: 20, weight average molecular weight: 10200) 1.0 g
・ Cyanine dye A (the above structure) 0.05 g
0.01 g of a dye having 1-naphthalenesulfonic acid anion as the counter anion of Victoria Pure Blue BOH
・ Fluorosurfactant 0.05g
(Megafuck F-177, manufactured by Dainippon Ink & Chemicals, Inc.)
・ Methyl ethyl ketone 9.0g
・ 9.0 g of 1-methoxy-2-propanol
Specific copolymer or comparative copolymer (compound described in Table 7) 0.2 g

<Evaluation of Reference Examples 53 and 54, Examples 55 to 60 and Comparative Examples 17 to 18>
The obtained lithographic printing plate precursor was used in Example 1 except that a developer (DP-4) of a developer (produced by Fuji Photo Film Co., Ltd.) containing an alkali metal silicate was used as the developer. Evaluation was performed in the same manner.

As shown in Table 7, the lithographic printing plate precursors of Examples 55 to 60 achieved improvement in the inking property, and there was no generation of sludge due to precipitates in the developer. From this, it can be seen that the lithographic printing plate precursor according to the present invention exhibits the excellent effects of the present invention not only in the case of having a multilayer structure but also having a single-layer recording layer. On the other hand, all of the lithographic printing plate precursors of Comparative Examples 17 to 18 that do not contain the specific copolymer according to the present invention are inferior in thickness to the examples and are caused by precipitates in the developer. Occurrence of sludge was observed.

Claims (2)

On the support, (a) a monomer represented by the following general formula (1), (b) a monomer represented by the following general formula (2), an acrylate ester having 20 or less carbon atoms, and a carbon atom having 20 or less carbon atoms. A positive lithographic printing plate precursor comprising a recording layer containing a polymer selected from methacrylic acid esters and a polymer compound having a copolymerization component and an infrared absorber.

In general formula (1), Rf is a fluoroalkyl group having 9 or more fluorine atoms or a perfluoroalkyl group-containing substituent, n represents 1 or 2, and R ¹ represents hydrogen or a methyl group. .

In the general formula (2), R ²¹ represents a hydrogen atom or a methyl group, R ²² represents a divalent hydrocarbon group having an aliphatic cyclic structure having 3 to 30 carbon atoms, and n represents 1. A represents an oxygen atom or —NR ²³ —, and R ²³ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.   The fluorine atom content contained in the polymer compound is in the range of 5 mmol / g to 30 mmol / g, and the content of the repeating unit derived from the monomer represented by the general formula (2) is the total molar amount of the polymer compound. 2. The positive planographic printing plate precursor according to claim 1, which is in the range of 0.1 mol% to 99 mol%.