JP2008265275A - Manufacturing method of original plate for lithographic printing plate and lithographic printing plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of an original plate for a lithographic printing plate which enables direct printing from digital data such as a computer by recording in use of a solid laser or a semiconductor laser light which irradiates an ultra violet light, a visible light, or an intra-red light, especially a simple process original plate for a lithographic printing plate which can be developed with an aqueous solution of lower than pH10 on a printing machine and has a good plate life and stain resistance, and also to provide a lithographic printing plate. <P>SOLUTION: The original plate for a lithographic printing plate includes a base and a photosensitive layer having a surface whose angle of contact with water droplet is 70°C or over, the base including a functional group X thereon. The functional group X contacts the functional group Y which can interact therewith, thereby forming a chemical bond with a compound having the functional group Y and making the compound adsorb onto the base surface, enabling lowering of the angle of contact with water droplet of the base surface down to 30°C or lower. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention relates to a so-called lithographic printing plate precursor capable of direct plate making using various lasers from a digital signal from a computer or the like, particularly a lithographic printing plate precursor of a simple processing type that does not require alkali development and a lithographic plate using the same. The present invention relates to a method for producing a printing plate.

Solid lasers, semiconductor lasers, and gas lasers that emit ultraviolet light, visible light, and infrared light having a wavelength of 300 nm to 1200 nm are easily available in high output and small size. It is very useful as a recording light source when making a plate directly from digital data. Various studies have been made on recording materials sensitive to these various laser beams. As a typical example, firstly, a positive recording material described in Patent Document 1 as a material that can be recorded by an infrared laser having a photosensitive wavelength of 760 nm or more. And acid-catalyst-crosslinked negative recording materials described in Patent Document 2. Secondly, there are many radical polymerization type negative recording materials described in Patent Document 3 and Patent Document 4 as recording materials compatible with ultraviolet light or visible light laser of 300 nm to 700 nm.

In addition, in a conventional lithographic printing plate precursor (hereinafter also referred to as PS plate), after exposure, a step (development treatment) for dissolving and removing the non-image part is indispensable, and the developed printing plate is washed with water, A post-treatment step is also necessary, in which treatment is performed with a rinse solution containing a surfactant or treatment with a desensitizing solution containing gum arabic or a starch derivative. The point that these additional wet treatments are indispensable is a big problem for the conventional PS plate. Even if the first half of the plate making process (image forming process) is simplified by the digital processing, the latter half (development process) is a complicated wet process.
The effect of simplification is insufficient.
Particularly in recent years, consideration for the global environment has become a major concern for the entire industry. In consideration of the environment, processing with a developing solution closer to the neutral range and a small amount of waste liquid are cited as problems. Furthermore, it is desirable to simplify the wet post-treatment or change to a dry treatment.

From this point of view, one method of eliminating the processing step is to mount the exposed printing original plate on the cylinder of the printing press, and supply dampening water and ink while rotating the cylinder to remove the non-printing original plate. There is a method called on-machine development that removes the image area. That is, after the printing original is exposed, it is mounted on a printing machine as it is, and the developing process is completed in a normal printing process.
Such a lithographic printing plate precursor suitable for on-press development has an image forming layer soluble in dampening water or an ink solvent, and is suitable for development on a printing press placed in a bright room. It is necessary to have good light room handling. However, with the conventional PS plate, it is practically impossible to satisfy such a requirement.
Therefore, in order to satisfy such requirements, a lithographic printing plate precursor in which an image forming layer in which thermoplastic hydrophobic polymer fine particles are dispersed in a hydrophilic binder polymer is provided on a hydrophilic support has been proposed. (For example, refer to Patent Document 5). In making the plate, it is exposed with an infrared laser, and the thermoplastic hydrophobic polymer fine particles are coalesced (fused) with heat generated by photothermal conversion to form an image. On-press development can be performed by supplying at least one of water and ink. This lithographic printing plate precursor also has handleability in a bright room because the photosensitive region is an infrared region.

However, an image formed by coalescence (fusion) of thermoplastic hydrophobic polymer fine particles has insufficient strength and has a problem in printing durability as a printing plate.
Further, a lithographic printing plate precursor including microcapsules encapsulating a polymerizable compound in place of the thermoplastic fine particles has been proposed (see, for example, Patent Documents 6 to 11). The original plate according to such a proposal has an advantage that the polymer image formed by the reaction of the polymerizable compound is superior in strength to the image formed by fusing fine particles.
In addition, since the polymerizable compound has high reactivity, many methods for isolating it using microcapsules have been proposed. It has been proposed to use a thermally decomposable polymer for the shell of the microcapsule.

However, the conventional lithographic printing plate precursors described in Patent Documents 5 to 11 above do not have sufficient printing durability of images formed by laser exposure, and further improvements are required. That is,
In these simple processing type lithographic printing plate precursors, a support having a highly hydrophilic surface is used in order to enable development with an aqueous solution having a pH of 10 or less or a dampening solution (usually almost neutral) on a printing press. As a result, the image area was easily peeled off from the substrate by dampening water during printing, and sufficient printing durability was not obtained. On the contrary, if the support surface is made hydrophobic, the ink also adheres to the non-image area during printing, and printing stains occur. Thus, it is extremely difficult to achieve both printing durability and stain resistance, and a simple processing type lithographic printing plate precursor having good stain resistance and sufficient printing durability has not been known so far. .
On the other hand, in Patent Document 12, (1) a polymer resin layer having a hydrophilic substituent that can be adsorbed to a support, and (2) an image recording layer that can be removed by oil-based ink and an aqueous component are arranged in this order. A planographic printing plate precursor having a contact angle of 50 ° or more and 100 ° or less on the surface of the polymer resin layer after coating on a support is described. It is described that when this polymer resin layer is supplied with oil-based ink and aqueous component on a printing machine to remove the unexposed portion, it is removed almost without remaining, so that good stain resistance can be obtained. .
US Pat. No. 4,708,925 JP-A-8-276558 U.S. Pat. No. 2,850,445 Japanese Patent Publication No. 44-20189 Japanese Patent No. 2938397 JP 2000-2111262 A JP 2001-277740 A JP 2002-29162 A JP 2002-46361 A JP 2002-137562 A JP 2002-326470 A JP 2006-15530 A

Accordingly, an object of the present invention is to provide a lithographic printing plate precursor capable of making a plate directly from digital data such as a computer by recording using a solid-state laser or semiconductor laser beam that emits ultraviolet light, visible light, or infrared light. An object of the present invention is to provide an aqueous solution having a pH of less than 10 and a simple processing type lithographic printing plate precursor that can be developed on a printing press with high printing durability and good stain resistance, and a method for producing a lithographic printing plate using the same.

As a result of intensive studies, the present inventors have determined that the water droplet contact angle value is obtained by treating a lithographic printing plate support having a surface with an air droplet contact angle of 70 ° or more with an aqueous solution having a pH of 2 to 10. 3
It has been found that the above-mentioned problems can be solved by using a lithographic printing plate support that lowers to 0 ° or less.
That is, the present invention is as follows.

(1) In a lithographic printing plate precursor comprising a support having a surface with an airborne water droplet contact angle of 70 ° or more and a photosensitive layer, the support has a compound having a functional group X on the surface, and the functional group X Adsorbs the compound having the functional group Y to the support surface by forming a chemical bond with the compound having the functional group Y by contacting with the compound having the functional group Y capable of interacting with the compound. And a lithographic printing plate precursor characterized by being a functional group capable of reducing the contact angle of water droplets on the surface of the support to 30 ° or less.
(2) The lithographic printing plate precursor as described in (1) above, wherein the functional group X is a functional group represented by the following general formula (0).

In the formula, R _{1 to} R ₃ each independently represents a monovalent substituent or a covalent bond composed of at least one atom selected from hydrogen, carbon, oxygen, nitrogen, sulfur, phosphorus, halogen, and silicon; Any two or more may be bonded to each other to form a ring. However, at least one of R _{1 to} R ₃ is a divalent linking group linked to a compound nucleus, which is composed of at least one atom selected from hydrogen, carbon, oxygen, nitrogen, sulfur, phosphorus, halogen and silicon. Represents.
(3) The functional group Y is —COOH, —SO ₃ H, —PO (OH) (OM), and —B (OH).
(OM) (M represents a functional group selected from hydrogen, metal cation, ammonium, phosphonium, iodonium, sulfonium, diazonium or azinium) The lithographic plate as described in (1) or (2) above A printing plate master.
(4) The lithographic printing plate precursor as described in (1) above, wherein the functional group X is a functional group having a positive charge, and the functional group Y is a functional group having a negative charge.
(5) The functional group X is a functional group represented by the following general formulas (1) to (5), and the functional group Y is represented by the following general formulas (6) to (8). The lithographic printing plate precursor as described in (4) above, which is a functional group.

In the formula, R _{1 to} R ₃ each independently represent hydrogen, an alkyl group, an aryl group, an alkenyl group, or an alkynyl group, L represents a divalent linking group linked to the compound mother nucleus, and Z ⁻ represents a pair Represents an anion.

In the formula, M1 ⁺ and M2 ⁺ each independently represent a counter cation, and L represents a divalent linking group linked to the compound mother nucleus.
(6) The lithographic printing plate precursor as described in (1) above, wherein the functional group X is a functional group having a negative charge, and the functional group Y is a functional group having a positive charge.
(7) The functional group X is a functional group represented by the following general formulas (9) to (11), and the functional group Y is represented by the following general formulas (12) to (16). The lithographic printing plate precursor as described in (6) above, which is a functional group.

In the formula, M1 ⁺ and M2 ⁺ each independently represent a counter cation, and L represents a divalent linking group linked to the compound mother nucleus.

In the formula, R _{1 to} R ₃ each independently represent hydrogen, an alkyl group, an aryl group, an alkenyl group, or an alkynyl group, L represents a divalent linking group linked to the compound mother nucleus, and Z ⁻ represents a pair Represents an anion.
(8) The lithographic printing plate precursor as described in any one of (1) to (7) above, wherein the photosensitive layer contains a binder polymer having an acid value of 0.3 mmol / g or less.
(9) The lithographic printing plate precursor as described in any one of (1) to (8) above, wherein the photosensitive layer contains a sensitizing dye having absorption at 350 to 1200 nm.
(10) The lithographic printing plate precursor as described in any one of (1) to (9) above, which has a protective layer on the photosensitive layer.
(11) Preparation of a lithographic printing plate in which the lithographic printing plate precursor according to any one of (1) to (10) above is subjected to image exposure and then developed with an aqueous solution having a pH of 2 to 10 to form a non-image part. In the method, lithographic printing characterized in that, during or after development, treatment with an aqueous solution containing the compound having the functional group Y reduces the contact angle of airborne water droplets on the support surface in the non-exposed area to 30 ° or less. Plate making method.

(12) The lithographic printing plate precursor according to any one of (1) to (10) above is subjected to image exposure with a laser having an oscillation wavelength of 350 to 1200 nm, and then the compound having the functional group Y is contained. A method for preparing a lithographic printing plate, comprising developing with an aqueous solution having a pH of 2 to 10 to remove a photosensitive layer in a non-exposed portion to form a non-image portion surface having an aerial water droplet contact angle of 30 ° or less.
(13) The lithographic printing plate precursor according to any one of (1) to (10) above is image-exposed with a laser having an oscillation wavelength of 350 to 1200 nm, and developed with an aqueous solution having a pH of 2 to 10. After removing the photosensitive layer in the non-exposed area, the surface is treated with an aqueous solution containing the compound having the functional group Y and having a pH of 2 to 10 to form a non-image area surface having an aerial water droplet contact angle of 30 ° or less. A method for producing a lithographic printing plate as a feature.
(14) The lithographic printing plate as described in any one of (11) to (13) above, wherein the exposed lithographic printing plate precursor is subjected to a heat treatment between the image exposure and development. Method.

According to the present invention, a lithographic printing original plate having high printing durability and excellent stain resistance that can be directly made by using various lasers from a digital signal of a computer or the like, particularly development using an alkaline aqueous solution is unnecessary. A simple processing type lithographic printing plate precursor and a method for producing a lithographic printing plate using the same are obtained.

The lithographic printing plate precursor according to the present invention has a photosensitive layer on a support having a surface with an aerial water droplet contact angle of 70 ° or more, and the support has a compound having a functional group X on the surface. The group X is brought into contact with a compound having a functional group Y capable of interacting with the group X, thereby forming a chemical bond with the compound having the functional group Y to form the compound having the functional group Y on the support surface. It is a functional group that can adsorb and reduce the contact angle of the water droplets on the support surface to 30 ° or less.

[Support]
First, the support used for the lithographic printing plate precursor according to the invention will be described in detail.
The support used in the present invention has a surface whose water droplet contact angle is 70 ° or more, but the water droplet contact angle is 30 ° when treated with a specific aqueous solution having a pH of 2 to 10. It has the following characteristics.

The support used in the present invention has a surface air droplet contact angle value of 70 ° or more, but p
After being developed with an aqueous solution containing a specific compound of H2 to 10, or after being developed with an aqueous solution of pH 2 to 10 and treated with an aqueous solution containing a specific compound of pH 2 to 10, the surface aerial water droplet contact angle Any support can be suitably used as long as the support has a property of lowering the value of 30 ° or less.

One example of a support having such properties has a compound having a functional group X on its surface, which is in contact with a compound having a functional group Y that can interact with it. This is a support that is a functional group that can reduce the contact angle of the water droplets on the surface of the support to 30 ° or less.
The functional group X existing on the surface of the support can interact with the functional group Y to cause an interaction and reduce the contact angle of the water droplets on the surface of the support to 30 ° or less. The interaction between the functional group X and the functional group Y includes that both react to form a bond. Here, the bond formed is preferably a chemical bond such as a hydrogen bond, an ionic bond, a covalent bond, or a coordination bond.
The compound having the functional group Y is fixed on the support by bonding of the functional group X and the functional group Y, and as a result, the contact angle of the water droplets on the support surface can be reduced to 30 ° or less.

Specific examples of the functional group X include basic functional groups such as a primary amino group, a secondary amino group, and a tertiary amino group.

  One preferable example of the compound having the functional group X includes a compound having a functional group represented by the following general formula (0).

In the formula, each of R _{1 to} R ₃ independently represents a monovalent group or a covalent bond composed of at least one atom selected from hydrogen, carbon, oxygen, nitrogen, sulfur, phosphorus, halogen, and silicon. May be bonded to each other to form a ring. However, at least one of R _{1 to} R ₃ is a divalent linking group that is linked to the compound nucleus and is composed of at least one atom selected from hydrogen, carbon, oxygen, nitrogen, sulfur, phosphorus, halogen, and silicon. To express.

In the general formula (0), hydrogen represented by R _{1 to} R ₃ , carbon, oxygen, nitrogen, sulfur, phosphorus,
A monovalent group consisting of at least one atom selected from halogen and silicon is -H,-
F, -Cl, -Br, -I,> C <, = C <, ≡C-, -O-, O =, -N <, -N =,
≡N, -S-, S =,> S <, ≡S≡, -P <, ≡P <,> Si <, = Si <, ≡Si-
And a monovalent group formed by combining these. Monovalent groups include hydrogen, alkyl groups [eg, methyl, ethyl, propyl, butyl, pentyl, hexyl,
Heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl,
s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group, 2-norbornyl group, chloromethyl group, Bromomethyl group, 2-chloroethyl group, trifluoromethyl group, methoxymethyl group, methoxyethoxyethyl group, allyloxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholino Propyl group, acetyloxymethyl group,

Benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxy Carbonylethyl group, allyloxycarbonylbutyl group, chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl -N-
(Sulfophenyl) carbamoylmethyl group, sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N -Methyl-N- (phosphonophenyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group, Tolylphosphonohexyl group, tolylphosphonatohexyl group, phosphonooxypropyl group, phosphonatoxybutyl group, benzyl group, phenethyl group,

α-methylbenzyl group, 1-methyl-1-phenylethyl group, p-methylbenzyl group, cinnamyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl group 2-propynyl group, 2-butynyl group, 3-butynyl group, etc.], aryl group [eg, phenyl group, biphenyl group, naphthyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group Chloromethylphenyl group,
Hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, Carboxyphenyl group, methoxycarbonylphenyl group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, nitrophenyl group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group,
Phosphonophenyl group, phosphonatophenyl group, etc.), heteroaryl group (for example, thiophene, thiathrene, furan, pyran, isobenzofuran, chromene, xanthene, phenoxazine, pyrrole, pyrazole, isothiazole, isoxazole, pyrazine, pyrimidine, Pyridazine, indolizine, isoindolizine, indoir, indazole, purine, quinolidine, isoquinoline, phthalazine, naphthyridine, quinazoline, sinoline, pteridine, carbazole, carboline, phenanthrine, acridine, perimidine, phenanthrolin, phthalazine, phenalazine, phenoxazine , A group derived from a hetero ring such as furazane, phenoxazine, etc.], an alkenyl group [eg, vinyl group, 1-propenyl group, 1-butenyl group, syn Mill group, 2-chloro-1-ethenyl group], an alkynyl group [
For example, ethynyl group, 1-propynyl group, 1-butynyl group, trimethylsilylethynyl group, etc.], halogen atom [—F, —Br, —Cl, —I], hydroxyl group,

Alkoxy group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio 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, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkylureido group, N'-arylureido group, N ', N'-diarylureido group, N'-alkyl-N'-arylureido group, N-alkylureido group, N-arylureido group, N'-alkyl-N-alkylureido Group, N′-alkyl-N-arylureido group, N ′, N′-dialkyl-N-alkylureido group, N ′, N′-dialkyl-N-arylureido group, N′-aryl-N-alkylureido group Group, N′-aryl-N-arylureido group, N ′, N′-diaryl-N-alkylureido group, N ′, N′-diaryl-N-arylureido group, N′-alkyl-N′-aryl -N-A Kiruureido group, N'- alkyl -N
'-Aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N- An alkoxycarbonylamino group, an N-aryl-N-aryloxycarbonylamino group,

Formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N -Alkyl-N-
Arylcarbamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (-SO3H) and its conjugate base group (hereinafter referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl Group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, Sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group , Phosphono group (-
PO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as phosphonate group), dialkyl phosphono group (—PO ₃ (alkyl) ₂ ), diaryl phosphono group (—PO ₃ (aryl) ₂ ), alkylaryl phosphine Phono group (—PO ₃ (alkyl) (aryl)), monoalkyl phosphono group (—PO ₃ H (alkyl))
) And conjugated base groups (hereinafter referred to as alkyl phosphonate groups), monoaryl phosphono groups (—PO ₃ H (aryl)) and conjugated base groups (hereinafter referred to as aryl phosphonate groups), phosphonooxy Group (—OPO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as “phosphonatooxy group”), dialkylphosphonooxy group (—OPO ₃ (alkyl) ₂ ), diarylphosphonooxy group (—OPO ₃ (aryl) ) ₂ ), an alkylarylphosphonooxy group (—OPO ₃ (
alkyl) (aryl)), monoalkylphosphonooxy group (—OPO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkylphosphonatooxy group), monoarylphosphonooxy group (—OPO ₃ H) (aryl)) and conjugated base groups thereof (hereinafter referred to as arylphosphonatooxy groups), cyano groups, nitro groups, and the like. Hydrogen atom, alkyl group, aryl group,
Alkenyl groups and alkynyl groups are preferred.

In the functional group represented by the general formula (0), the divalent linking group linked to the compound nucleus is a divalent group formed by removing one constituent atom from the monovalent group. is there.
As the compound mother nucleus having the functional group represented by the general formula (0), any organic compound mother nucleus having a molecular weight of 150 or more can be suitably used, but a polymer compound having a mass average molecular weight of 1000 or more. It is preferably a mother nucleus, more preferably a polymer compound mother nucleus having a mass average molecular weight of 5000 or more, and particularly preferably a polymer compound mother nucleus having a mass average molecular weight of 10,000 or more. As the polymer compound core, known resins such as acrylic resin, methacrylic resin, styrene resin, ester resin, amide resin, urethane resin, urea resin, vinyl resin, novolac resin, epoxy resin, and carbonate resin may be used. Acrylic resin, methacrylic resin, styrene resin, ester resin, amide resin, urethane resin, urea resin, and vinyl resin are preferable, and acrylic resin, methacrylic resin, styrene resin, and urethane resin are more preferable.

  The amount of the general formula (0) in the compound having the functional group represented by the general formula (0) is preferably 0.01 mmol / g or more and 50 mmol / g or less, and 0.05 mmol / g or more and 25 mmol / g or less. Is more preferable, and 0.1 mmol / g or more and 10 mmol / g or less is particularly preferable. The functional group represented by the general formula (0) may be contained in two or more types of compounds.

  The compound having a functional group represented by the general formula (0) preferably further has a functional group that interacts with the surface of the support. By having a functional group that interacts with the surface of the support, the printing durability of the image area and the stain resistance of the non-image area are further improved. Such an interactive functional group can be appropriately selected depending on the support used. Among them, when using an aluminum support conventionally used as a support for a lithographic printing plate, specific functional groups differ depending on the surface treatment, but a phosphate group and its base, a phosphonic acid group and its base, Functional groups such as an ammonium group, a siloxane group, a β-dicarbonyl group, a carboxylic acid group and a base thereof can be mentioned. Preferred are a phosphate group, a phosphonate group, an ammonium group, a siloxane group, a β-dicarbonyl group, and a carboxylate group. These functional groups can be used in combination.

  In the compound having the functional group represented by the general formula (0), the introduction amount of the functional group that interacts with the support surface is preferably 0.01 mmol / g or more and 10 mmol / g or less, and 0.05 mmol / g or more. 5 mmol / g or less is more preferable, and 0.1 mmol / g or more and 3 mmol / g or less is particularly preferable.

The compound having a functional group represented by the general formula (0) preferably further has a functional group that interacts with the photosensitive layer. By having a functional group that interacts with the photosensitive layer, printing durability is further improved. Such an interactive functional group can be appropriately selected depending on the photosensitive layer to be used. When a radical polymerization type photosensitive layer is used, examples of the interactive functional group include a radical polymerizable unsaturated bond. Further, when a positive photosensitive layer using a novolac resin is used, examples of the interacting functional group include a hydrogen-accepting functional group involved in hydrogen bonding such as a polyethylene oxide chain, a phenolic hydroxyl group, and a pyridine group. These functional groups can be used in combination. The amount of the functional group that interacts with the photosensitive layer is preferably from 0.01 mmol / g to 10 mmol / g, more preferably from 0.05 mmol / g to 5 mmol / g, and from 0.1 mmol / g to 3 mmol / g. The following are particularly preferred:
Specific examples of the compound having a functional group represented by the general formula (0) used in the present invention are shown below. The present invention is not limited to these.

The compound having a functional group represented by the general formula (0) used in the present invention may be used alone or in combination of two or more.
The amount of the compound having the functional group represented by the general formula (0) on the support is preferably 1 mg / m ² or more and 100 mg / m ² or less from the viewpoint of improving printing durability and stain resistance. m ² or more and 80 mg / m ² or less is more preferable, and 3 mg / m ² or more and 50 mg / m ² or less is particularly preferable.

Specific examples of the functional group Y that interacts with the functional group X represented by the general formula (0) include —COOH, —SO ₃ H, —PO (OH) (OM), and —B (OH). ) (OM) (M represents hydrogen, metal cation, ammonium, phosphonium, iodonium, sulfonium, diazonium or azinium) and the like. In this case, the functional group X and the functional group Y form an ionic bond by acid-base interaction, and as a result, when the compound having the functional group Y is fixed on the support and the contact angle of the water droplets on the surface of the support decreases. Conceivable.
The method for bringing the compound having the functional group X represented by the general formula (0) into contact with the compound having the functional group Y will be described in detail later in connection with a method for preparing a lithographic printing plate.

Other preferred examples of the compound having the functional group X include compounds having a functional group having a positive charge. A compound having a functional group having a positive charge as the functional group X forms an ionic bond by interacting with a compound having a functional group having a negative charge as the functional group Y. As a result, the compound having the functional group Y It is considered that the contact angle of the water droplets on the surface of the support fixed on the support is lowered.
Examples of the compound having a functional group having a positive charge include compounds having a functional group represented by the following general formulas (1) to (5).

In the formula, R _{1 to} R ₃ each independently represent hydrogen, an alkyl group, an aryl group, an alkenyl group, or an alkynyl group, L represents a divalent linking group linked to the compound mother nucleus, and Z ⁻ represents a pair Represents an anion.

Of the compounds having the functional group represented by the general formulas (1) to (5), the compound having the functional group represented by the general formula (1) or (2) is preferable, and represented by the general formula (1). Particularly preferred are compounds having functional groups.
In formulas (1) to _(5), the alkyl group represented by R 1 to R _3, aryl group, alkenyl group and alkynyl groups, alkyl groups as described for _R 1 to R ₃ in the general formula (0) , Aryl group, alkenyl group and alkynyl group.

  The divalent linking group represented by L is 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 100 hydrogen atoms. , And from 0 to 20 sulfur atoms. More specifically, the following structural units may be combined.

  When the linking group represented by L has a substituent, examples of the substituent include alkyl groups having 1 to 20 carbon atoms such as methyl and ethyl, aryl groups having 6 to 16 carbon atoms such as phenyl and naphthyl, hydroxyl groups, Carboxyl group, sulfonamide group, N-sulfonylamide group, acyloxy group having 1 to 6 carbon atoms such as acetoxy, alkoxy group having 1 to 6 carbon atoms such as methoxy and ethoxy, halogen such as chlorine and bromine Examples include atoms, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl, ethoxycarbonyl, cyclohexyloxycarbonyl, and cyano groups.

Any counter anion represented by Z ⁻ can be used as long as it is an anion. Specifically, halogen ions (F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ ), nitrate ions (NO ₃ ⁻ ), sulfate ions (SO ₄ ²⁻ ), hydrogen sulfate ions (HSO ₄ ⁻ ), phosphate ions (PO ₄ ³⁻ ), hydrogen phosphate ion (HPO ₄ ²⁻ ), dihydrogen phosphate ion (H ₂ PO ⁴⁻ ), hypohalite ion (ClO ⁻ , BrO ⁻ etc.), halite ion ion ( ClO ₂ ⁻ , BrO ₂ ⁻ etc.), halogenate ions (ClO ₃ ⁻ , BrO ₃ ⁻ etc.), perhalogenate ions (ClO ₄ ⁻ , BrO ₄ ⁻ , IO ₄ ⁻ etc.), tetrahalogen borate ions (BF ₄ ^- etc.), tetraarylborate ion (Ph ₄ B ^-, etc.), hexa halogen phosphate ion (PF ₆ ^-, etc.), and the carboxylic acid ion represented by the following structural formula, benzoic acid anion ,, carbonic acid amide ion, sulfonate Ion, sulfinate ion, thiosulfonate ion, sulfonimide On, sulfate ions, sulfate amide ion, phosphoric acid ester ion, phosphate diester ion, phosphonate ion, phosphonate ion Ageraru. Of these, perhalogenate ions, hexahalogen phosphate ions, tetrahalogen borate ions, tetraaryl borate ions, sulfonate ions, sulfinate ions, carboxylate ions, halogen ions, nitrate ions, sulfate ions, and sulfonimide ions are preferred. Sulfonate ion, carboxylate ion, tetrafluoroborate ion, hexafluorophosphate ion, and sulfonimide ion are more preferable.

  As the compound mother nucleus having the functional group represented by the general formulas (1) to (5), any organic compound mother nucleus having a molecular weight of 150 or more can be preferably used, but the mass average molecular weight is 1000. The above polymer compound mother nucleus is preferable, a polymer compound mother nucleus having a mass average molecular weight of 5000 or more is more preferable, and a polymer compound mother nucleus having a mass average molecular weight of 10,000 or more is particularly preferable. As the polymer compound core, known resins such as acrylic resin, methacrylic resin, styrene resin, ester resin, amide resin, urethane resin, urea resin, vinyl resin, novolac resin, epoxy resin, and carbonate resin may be used. Acrylic resin, methacrylic resin, styrene resin, ester resin, amide resin, urethane resin, urea resin, and vinyl resin are preferable, and acrylic resin, methacrylic resin, styrene resin, and urethane resin are more preferable.

  The amount of the functional group represented by the general formulas (1) to (5) in the compound having the functional group represented by the general formulas (1) to (5) is 0.01 mmol / g or more and 50 mmol / g. Or less, more preferably 0.05 mmol / g or more and 25 mmol / g or less, and particularly preferably 0.1 mmol / g or more and 10 mmol / g or less. The functional groups represented by the general formulas (1) to (5) may be included in two or more types of compounds.

  The compound having a functional group represented by the general formulas (1) to (5) preferably further has a functional group that interacts with the support surface. By having a functional group that interacts with the surface of the support, the printing durability of the image area and the stain resistance of the non-image area are further improved. For the interactive functional group, the description regarding the functional group that interacts with the support surface described in the compound having the functional group represented by the general formula (0) can be used.

  The compound having a functional group represented by the general formulas (1) to (5) preferably further has a functional group that interacts with the photosensitive layer. By having a functional group that interacts with the photosensitive layer, printing durability is further improved. For the interactive functional group, the description regarding the functional group that interacts with the surface of the photosensitive layer described above in the compound having the functional group represented by the general formula (0) can be used.

  Specific examples of the compound having a functional group represented by the general formulas (1) to (5) used in the present invention are shown below. The present invention is not limited to these.

The compounds having functional groups represented by the general formulas (1) to (5) used in the present invention may be used alone or in combination of two or more.
The amount of the compound having the functional group represented by the general formulas (1) to (5) on the support is 1 mg / m ² or more and 100 mg / m ² or less from the viewpoint of improving printing durability and stain resistance. It is preferably 2 mg / m ² or more and 80 mg / m ² or less, more preferably 3 mg / m ² or more and 50 mg / m ² or less.

  As the functional group Y that interacts with the functional group X represented by the general formulas (1) to (5), specifically, for example, functional groups represented by the following general formulas (6) to (8) Is mentioned.

In the formula, M1 ⁺ and M2 ⁺ each independently represent a counter cation, and L represents a divalent linking group linked to the compound mother nucleus.

In the general formulas (6) to (8), specific examples of counter cations represented by M1 ⁺ and M2 ⁺ include hydrogen ions, metal ions (Na ⁺ , K ⁺ , Li ⁺ , Ca ²⁺ , Mg ²⁺ , Fe ²⁺ , Cu ^+, etc.), ammonium ions, iodonium ions, phosphonium ions, sulfonium ions, diazonium ions, azinium ions, and hydrogen ions, metal ions, ammonium ions, and phosphonium ions are preferred.

  Details of the divalent linking group represented by L are the same as those of the divalent linking group represented by L in the general formulas (1) to (5).

  The method of bringing the compound having the functional group X represented by the general formulas (1) to (5) into contact with the compound having the functional group Y represented by the general formulas (6) to (8) will be described later in lithographic printing. This will be described in detail in relation to the method for producing the plate.

Still another preferred example of the compound having the functional group X includes a compound having a functional group having a negative charge. A compound having a functional group having a negative charge as the functional group X forms an ionic bond by interacting with a compound having a functional group having a positive charge as the functional group Y. As a result, the compound having the functional group Y It is considered that the contact angle of the water droplets on the surface of the support fixed on the support is lowered.
Examples of the compound having a functional group having a negative charge include compounds having functional groups represented by the following general formulas (9) to (11).

^Wherein, M1 +, M2 ⁺ and L, ^M1 + in the general formula (6) to (8), the same meanings as M2 ⁺ and L.

In the general formulas (9) to (11), details of the counter cation represented by M1 ⁺ and M2 ⁺ and the divalent linking group represented by L are represented by M1 ⁺ in the general formulas (6) to (8). , The same as the counter cation represented by M2 ⁺ and the divalent linking group represented by L.

  As the compound mother nucleus having the functional groups represented by the general formulas (9) to (11), any organic compound mother nucleus having a molecular weight of 150 or more can be preferably used, but the mass average molecular weight is 1000. The above polymer compound mother nucleus is preferable, a polymer compound mother nucleus having a mass average molecular weight of 5000 or more is more preferable, and a polymer compound mother nucleus having a mass average molecular weight of 10,000 or more is particularly preferable. As the polymer compound core, known resins such as acrylic resin, methacrylic resin, styrene resin, ester resin, amide resin, urethane resin, urea resin, vinyl resin, novolac resin, epoxy resin, and carbonate resin may be used. Acrylic resin, methacrylic resin, styrene resin, ester resin, amide resin, urethane resin, urea resin, and vinyl resin are preferable, and acrylic resin, methacrylic resin, styrene resin, and urethane resin are more preferable.

  The amount of the functional group represented by the general formulas (9) to (11) in the compound having the functional group represented by the general formulas (9) to (11) is 0.01 mmol / g or more and 50 mmol / g. Or less, more preferably 0.05 mmol / g or more and 25 mmol / g or less, and particularly preferably 0.1 mmol / g or more and 10 mmol / g or less. The functional groups represented by the general formulas (9) to (11) may include two or more types.

  The compound having a functional group represented by the general formulas (9) to (11) used in the present invention preferably further has a functional group that interacts with the support surface. By having a functional group that interacts with the surface of the support, the printing durability of the image area and the stain resistance of the non-image area are further improved. For the interactive functional group, the description regarding the functional group that interacts with the support surface described in the compound having the functional group represented by the general formula (0) can be used.

  The compound having a functional group represented by the general formulas (9) to (11) preferably further has a functional group that interacts with the photosensitive layer. By having a functional group that interacts with the photosensitive layer, printing durability is further improved. For the interactive functional group, the description regarding the functional group that interacts with the surface of the photosensitive layer described above in the compound having the functional group represented by the general formula (0) can be used.

  Specific examples of the compound having a functional group represented by the general formulas (9) to (11) used in the present invention are shown below. The present invention is not limited to these.

The compounds having the functional groups represented by the general formulas (9) to (11) used in the present invention may be used alone or in combination of two or more.
The amount of the compound having the functional group represented by the general formulas (9) to (11) on the support is 1 mg / m ² or more and 100 mg / m ² or less from the viewpoint of improving printing durability and stain resistance. It is preferably 2 mg / m ² or more and 80 mg / m ² or less, more preferably 3 mg / m ² or more and 50 mg / m ² or less.

    As the functional group Y that interacts with the functional group X represented by the general formulas (9) to (11), specifically, for example, functional groups represented by the following general formulas (12) to (16) Is mentioned.

_{Wherein, R} 1 _{~R 3,} L and Z ^- is, _R 1 ~R 3, L and Z in the general formula (1) to (5) ^- synonymous.

In the general formulas (12) to (16), details of each group represented by R _{1 to} R ₃ and the divalent linking group represented by L are represented by R ₁ in the general formulas (1) to (5). is the same as the divalent linking Moto及represented by each group and L represented by to R _3.

Any counter anion represented by Z ⁻ can be used as long as it is an anion. Specific examples include the anions described for the counter anions in the above general formulas (1) to (5), such as perhalogenate ions, hexahalogen phosphate ions, tetrahalogen borate ions, tetraaryl borate ions, and sulfonic acids. Ion, sulfinate ion, carboxylate ion, halogen ion, nitrate ion, sulfate ion, sulfonimide ion are preferred, sulfonate ion, carboxylate ion, tetrafluoroborate ion, hexafluorophosphate ion, sulfonimide ion, sulfate ion, Halogen ions are more preferred.

  The method of bringing the compound having the functional group X represented by the general formulas (9) to (11) into contact with the compound having the functional group Y represented by the general formulas (12) to (16) will be described later in lithographic printing. This will be described in detail in relation to the method for producing the plate.

The preparation of the support having the compound having the functional group X on the surface is performed, for example, by coating the support substrate with the compound having the functional group X on the support substrate, into a solution containing the compound having the functional group X on the support substrate. It can be performed by a conventional method such as dipping. Specifically, the compound having the functional group represented by the general formula (1) is converted into an appropriate solvent such as toluene, xylene, benzene, hexane, heptane, cyclohexane, diethyl ether, diisopropyl ether, dimethoxyethane, anisole, Tetrahydrofuran, methylene chloride, chloroform, ethylene dichloride, chlorobenzene, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, acetone, methyl ethyl ketone, cyclohexanone, methanol, ethanol, propanol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2 -Methoxyethyl acetate, 1-methoxy-2-propyl acetate, N-dimethylacetamide, N, N-dimethylformamide, tetramethylurea, N-methylpyrrole Dissolve or disperse in water, dimethyl sulfoxide, sulfolane, γ-butyl lactone, water, etc., and if necessary, add a component such as a surfactant to prepare a coating solution or immersion solution, and apply this to the support or A method of immersing and drying the support is used. A person skilled in the art can appropriately select a method for preparing a coating solution and a dipping solution, a coating method, a dipping method, a drying method, and the like.

A support having a compound having a functional group X on its surface has an air contact angle of 70 ° on the surface.
That's it. The aerial water droplet contact angle on the support surface can be measured as follows. That is, in an atmosphere of 25 ° C., 1 to 3 μL of distilled water was deposited on the support to be measured, and after 60 seconds had passed for stabilization, contact angle meter DAC- manufactured by Kyowa Interface Science Co., Ltd. VZ
Measure the water contact angle in the air using a mold.
The aerial water droplet contact angle on the surface of the support is preferably 75 ° or more, and more preferably 80 ° or more.

The support used for the lithographic printing plate precursor according to the present invention is not particularly limited except for the above-mentioned properties.
Any plate-like support that is dimensionally stable may be used. For example, paper, paper laminated with plastic (eg, 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 or plastic film on which the above-mentioned metal is laminated or deposited. Preferable supports include a polyester film and an aluminum plate. Among these, an aluminum plate that has good dimensional stability and is relatively inexpensive is preferable.

The aluminum plate is a pure aluminum plate, an alloy plate containing aluminum as a main component and containing a trace amount of different elements, or a plastic laminated on a thin film of aluminum or an aluminum alloy. 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 preferably 10% by mass or less. In the present invention, a pure aluminum plate is preferable, but completely pure aluminum is difficult to manufacture in terms of refining technology.
It may contain a slightly different element. The composition of the aluminum plate is not specified, and a publicly known material can be used as appropriate.

The thickness of the aluminum support is preferably from 0.1 to 0.6 mm, preferably from 0.15 to 0.
It is more preferable that it is 4 mm, and it is still more preferable that it is 0.2-0.3 mm.

Prior to using the aluminum plate, it is preferable to perform a surface treatment such as roughening treatment or anodizing treatment. By the surface treatment, the width of the contact angle change of the present invention is increased, the adhesion between the photosensitive layer and the support is easily ensured, and the stain resistance is improved. Prior to roughening the aluminum plate, a degreasing treatment with a surfactant, an organic solvent, an alkaline aqueous solution or the like 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, mechanical surface roughening treatment, electrochemical surface roughening treatment (electrochemical surface roughening treatment that dissolves the surface), chemical treatment, etc. Surface roughening treatment (roughening treatment that chemically selectively dissolves the surface).
As a method for the mechanical surface roughening treatment, 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.
Examples of the electrochemical surface roughening treatment include a method in which an alternating current or a direct current is used in an electrolytic solution containing an acid such as hydrochloric acid or nitric acid. Another example is a method using a mixed acid as described in JP-A-54-63902.

The surface-roughened aluminum plate is subjected to an alkali etching treatment using an aqueous solution of potassium hydroxide, sodium hydroxide or the like, if necessary, further neutralized, and if desired, wear resistant. In order to increase the anodic oxidation treatment.

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, hydrochloric 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 conditions for anodizing treatment vary depending on the electrolyte used and 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
-60 A / dm ² , voltage 1-100 V, electrolysis time 10 seconds to 5 minutes are preferred. The amount of the anodic oxide film to be formed is preferably 1.0 to 5.0 g / m ² , and 1.5 to 4.
More preferably, it is 0 g / m ² . Within this range, good printing durability and good scratch resistance of the non-image area of the lithographic printing plate can be obtained.

As the support used in the present invention, the substrate having the above-mentioned surface treatment and having an anodized film may be used as it is, but the adhesion with the upper layer, the hydrophilicity after the treatment with the aqueous solution of pH 2 to 10 of the present invention, In order to further improve dirt resistance, heat insulation, etc., if necessary, JP-A-2001-2
53181 and JP-A-2001-322365, such as micropore enlargement treatment, micropore sealing treatment, and surface hydrophilization treatment immersed in an aqueous solution containing a hydrophilic compound. It can be selected as appropriate. Of course, these enlargement processing and sealing processing are not limited to those described above, and any conventionally known method can be performed.

Sealing treatment includes vapor sealing, single treatment with zirconic fluoride, treatment with an aqueous solution containing an inorganic fluorine compound such as treatment with sodium fluoride, vapor sealing with addition of lithium chloride, sealing with hot water. Hole processing is also possible.
Of these, sealing treatment with an aqueous solution containing an inorganic fluorine compound, sealing treatment with water vapor, and sealing treatment with hot water are preferable.

As hydrophilization treatment, U.S. Pat. Nos. 2,714,066, 3,181,461,
There are alkali metal silicate methods as described in the specifications of US Pat. Nos. 3,280,734 and 3,902,734. In this method, the support is immersed in an aqueous solution such as sodium silicate or electrolytically treated. In addition, the method of treating with potassium zirconate fluoride described in JP-B 36-22063, US Pat. No. 3,276
No. 868, No. 4,153,461 and No. 4,689,272, and the like.

Moreover, when using a polyester film etc. as a support body of this invention, it is preferable to provide an antistatic layer in one side or both sides. In the case where the antistatic layer is provided between the support and the layer containing the compound having the functional group X, it contributes to improving the adhesion with the layer containing the compound having the functional group X. As the antistatic layer, described in JP-A-2002-79772,
A polymer layer in which metal oxide fine particles and a matting agent are dispersed can be used.

The support preferably has a center line average roughness of 0.10 to 1.2 μm. Within this range, good adhesion to the photosensitive layer, good printing durability and good stain resistance can be obtained.
The color density of the support is preferably 0.15 to 0.65 as the reflection density value. Within this range, good image formability by preventing halation during image exposure and good plate inspection after development can be obtained.

The support according to the present invention can be a lithographic printing plate precursor by forming a photosensitive layer thereon. In particular, when used as a support for a simple development type lithographic printing plate using a photosensitive layer that can be developed with an aqueous solution having a pH of 2 to 10, a lithographic printing plate precursor exhibiting excellent printing durability and antifouling performance is obtained. Can be provided.

[Lithographic printing plate precursor]
The lithographic printing plate precursor according to the invention is characterized in that a photosensitive layer is provided on a support having a surface with an airborne water droplet contact angle of 70 ° or more. A lithographic printing plate precursor has the following characteristics mainly due to the characteristics of its photosensitive layer (hereinafter also referred to as an image forming layer). 1. radical polymerization type lithographic printing plate precursor; 2. heat fusion type lithographic printing plate precursor; There are polar conversion type lithographic printing plate precursors, and the lithographic printing plate precursor of the present invention may be any of these.
First, a radical polymerization type lithographic printing plate precursor will be described.
[Photosensitive layer]
The photosensitive layer in the radical polymerization type lithographic printing plate precursor contains a polymerizable compound, a polymerization initiator, a binder polymer, a sensitizing dye, and other components. Below, each component which comprises a photosensitive layer is demonstrated.

(Polymerizable compound)
The polymerizable compound used in the photosensitive layer in the present invention is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and is a compound having at least one terminal ethylenically unsaturated bond, preferably two or more. To be elected. Such a compound group is widely known in the industrial field, and can be used without any particular limitation in the present invention. These have chemical forms such as monomers, prepolymers, ie dimers, trimers and oligomers, or copolymers thereof and mixtures thereof. Examples of monomers include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters and amides thereof, preferably unsaturated carboxylic acids. An ester of an acid and an aliphatic polyhydric alcohol compound and an amide of an unsaturated carboxylic acid and an aliphatic polyamine compound are used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, amino group or mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and a monofunctional or polyfunctional compound. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or In addition, a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate,
Hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate Sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, isocyanuric acid ethylene oxide (EO) modified triacrylate, polyester acrylate oligomer, and the like.

Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy- 2-hydroxypro ) Phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate. As crotonic acid ester,
Examples include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

Examples of other esters include, for example, Japanese Patent Publication No. 51-47334, Japanese Patent Laid-Open No. 57-19.
The aliphatic alcohol esters described in JP 6231 and the aromatic skeletons described in JP 59-5240, JP 59-5241, and JP 2-226149 Those having an amino group described in JP-A-1-165613 are also preferably used. Furthermore, the ester monomers described above can also be used as a mixture.

Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like. Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B No. 54-21726.

Further, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable. Specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinylurethane compound containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (A) to a polyisocyanate compound having two or more isocyanate groups Etc.

_{CH 2 = C (R 4)} COOCH 2 CH (R 5) OH (A)
(However, R ₄ and R ₅ represent H or CH _3. )

JP-A-51-37193, JP-B-2-32293, JP-B-2-16
No. 765, urethane acrylates described in Japanese Patent Publication No. 765, and Japanese Patent Publication No. 58-4986.
No. 0, JP-B 56-17654, JP-B 62-39417, JP-B 62
Urethane compounds having an ethylene oxide skeleton described in Japanese Patent No. -39418 are also suitable. Furthermore, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are used. Depending on the case, it is possible to obtain a photopolymerizable composition excellent in the photosensitive speed.

Other examples include polyester acrylates, epoxy resins and (meth) acrylic acid as described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, and JP-A-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as reacted epoxy acrylates. In addition, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337, and JP-B-1-40336, vinylphosphonic acid compounds described in JP-A-2-25493, and the like are also included. Can be mentioned. In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, 300-3
Those introduced as photocurable monomers and oligomers on page 08 (1984) can also be used.

About these polymerizable compounds, the details of usage such as the structure, single use or combination, addition amount, etc. can be arbitrarily set according to the performance design of the final lithographic printing plate precursor. For example, it is selected from the following viewpoints.
From the viewpoint of sensitivity, a structure having a large unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, in order to increase the strength of the image portion, that is, the cured film, those having three or more functionalities are preferable, and further, different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether type). A method of adjusting both sensitivity and strength by using a compound) is also effective.
In addition, the compatibility and dispersibility with other components in the photosensitive layer (for example, binder polymer, polymerization initiator, colorant, etc.), the selection and use method of the polymerizable compound is an important factor. ,
The compatibility may be improved by using a low-purity compound or using two or more kinds in combination. Also,
A specific structure may be selected for the purpose of improving adhesion to a support or a protective layer described later.

The polymerizable compound is preferably used in the range of 5 to 80% by mass, more preferably 25 to 75% by mass, based on the total solid content of the photosensitive layer. These may be used alone or in combination of two or more. In addition, the usage of the polymerizable compound is such that the polymerization inhibition with respect to oxygen is large or small,
An appropriate structure, blending, and addition amount can be arbitrarily selected from the viewpoints of resolution, fogging property, refractive index change, surface adhesiveness, and the like, and in some cases, a layer configuration / coating method such as undercoating or overcoating can be performed.

(Polymerization initiator)
The polymerization initiator used in the present invention is a compound that initiates and accelerates the polymerization of a compound having a polymerizable unsaturated group by generating radicals by light or thermal energy. Such a polymerization initiator can be appropriately selected from known polymerization initiators and compounds having a bond having a small bond dissociation energy.

Examples of the polymerization initiator include organic halogen compounds, carbonyl compounds, organic peroxides, azo compounds, azide compounds, metallocene compounds, hexaarylbiimidazole compounds, organic boron compounds, disulfone compounds, oxime ester compounds, onium salts. Compounds.

Specific examples of the organic halogen compound include Wakabayashi et al., “Bull Chem.
c Japan "42, 2924 (1969), U.S. Pat. No. 3,905,815, JP-B 46-4605, JP-A 48-36281, JP-A 53-133428, JP-A 55-32070. JP, 60-609736, JP 61-169835,
JP-A-61-169837, JP-A-62-258241, JP-A-62-212401, JP-A-63-70243, JP-A-63-298339, P. Hutt,
“Journal of Heterocyclic Chemistry”, 1 (No.
3) The compound as described in (1970) is mentioned. Of these, oxazole compounds and S-triazine compounds substituted with a trihalomethyl group are preferred.

More preferably, at least one mono, di, or trihalogen substituted methyl group is s
-An s-triazine derivative bonded to a triazine ring and an oxadiazole derivative bonded to an oxadiazole ring. Specifically, for example, 2,4,6-tris (monochloromethyl) -s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -S-triazine, 2-methyl-4,6-
Bis (trichloromethyl) -s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloro Methyl) -s-triazine, 2- (3,4-epoxyphenyl) -4, 6-
Bis (trichloromethyl) -s-triazine, 2- [1- (p-methoxyphenyl) -2
, 4-Butadienyl] -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxystyryl) -4,6 -Bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (Trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2-phenylthio-4,6
-Bis (trichloromethyl) -s-triazine, 2-benzylthio-4,6-bis (trichloromethyl) -s-triazine, 2,4,6-tris (dibromomethyl) -s-triazine, 2,4,6 -Tris (tribromomethyl) -s-triazine, 2-methyl-4,6
Examples include -bis (tribromomethyl) -s-triazine, 2-methoxy-4,6-bis (tribromomethyl) -s-triazine, the following compounds, and the like.

Examples of the carbonyl compound include benzophenone, Michler ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone and other benzophenone derivatives, 2,2-dimethoxy- 2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1- Hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4 ′
Acetophenone derivatives such as-(methylthio) phenyl) -2-morpholino-1-propanone, 1,1,1-trichloromethyl- (p-butylphenyl) ketone, thioxanthone,
Thioxanthone derivatives such as 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, ethyl p-dimethylaminobenzoate, p- Examples thereof include benzoic acid ester derivatives such as ethyl diethylaminobenzoate.

As the azo compound, for example, an azo compound described in JP-A-8-108621 can be used.

Examples of the organic peroxide include trimethylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (tert-butylperoxy) -3,3.
, 5-trimethylcyclohexane, 1,1-bis (tert-butylperoxy) cyclohexane, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroper Oxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,
1,3,3-tetramethylbutyl hydroperoxide, tert-butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2,5-oxa Noyl peroxide, succinic peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, dimethoxy Isopropyl peroxycarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, tert-butyl peroxyacetate, tert-butyl peroxypivalate, tert-butyl peroxyneodecanoate, ter -Butyl peroxyoctanoate, tert-butyl peroxylaurate, tersyl carbonate, 3,3 ', 4,4'-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3', 4,4 '-Tetra- (t-hexylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone, carbonyldi (t-butylperoxydihydrogen diphthalate) , Carbonyldi (t-hexylperoxydihydrogen diphthalate) and the like.

Examples of the metallocene compounds include JP-A-59-152396 and JP-A-61-15.
No. 1197, JP-A 63-41484, JP-A 2-249, JP-A 2-
Various titanocene compounds described in Japanese Patent No. 4705 and JP-A-5-83588, for example,
Di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-
Bis-2,6-difluorophen-1-yl, di-cyclopentadienyl-Ti-bis-
2,4-di-fluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,
4,6-trifluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,
3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, di-methylcyclopentadienyl -Ti-bis-2,6-difluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4,6-trifluorophen-1-yl, di-methylcyclopentadienyl- Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1
-Yl, bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyr-1-
Yl) phenyl) titanium, JP-A-1-304453, JP-A-1-152109
And iron-arene complexes described in the Japanese Patent Publication.

Examples of the hexaarylbiimidazole compound include Japanese Patent Publication No. 6-29285, U.S. Pat. Nos. 3,479,185, 4,311,783, and 4,622.
Various compounds described in the specification of No. 286, specifically, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′- Bis (o-bromophenyl)) 4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (
o, p-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,
2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (m-methoxyphenyl) biidazole, 2,2'-bis (o, o'-dichlorophenyl) -4,4', 5 , 5'-
Tetraphenylbiimidazole, 2,2′-bis (o-nitrophenyl) -4,4 ′, 5
5′-tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl) -4,4 ′
, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-trifluorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, and the like.

Examples of the organoboron compound include, for example, JP-A-62-143044 and JP-A-62-2.
150242, JP-A-9-188865, JP-A-9-188686, JP-A-9-1
No. 88710, JP-A No. 2000-131737, JP-A No. 2002-107916,
Japanese Patent No. 2764769, Japanese Patent Application Laid-Open No. 2002-116539, and Kunz
Martin "Rad Tech '98. Proceeding April 19-2.
2, 1998, Chicago "etc., JP-A-6-157623
Organoboron sulfonium complexes or organoboron oxosulfonium complexes described in JP-A-6-175564, JP-A-6-175561, JP-A-6-1755.
No. 54, JP-A-6-175553, organoboron iodonium complexes, JP-A-9-188710, organoboron phosphonium complexes, JP-A-6-34801
No. 1, JP-A-7-128785, JP-A-7-140589, JP-A-7-
Examples thereof include organoboron transition metal coordination complexes such as 306527 and JP-A-7-292014.

Examples of the disulfone compound include JP-A Nos. 61-166544 and 2003-3.
And compounds described in Japanese Patent No. 28465.

Examples of the oxime ester compounds include JCS Perkin II (1979) 1653-1660), JCS
Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202
-232, compounds described in JP-A No. 2000-66385, and compounds described in JP-A No. 2000-80068. Specific examples include compounds represented by the following structural formula.

Examples of the onium salt compound include S.I. I. Schlesinger, Photo
ogr. Sci. Eng. , 18, 387 (1974), T.A. S. Bal et al,
Polymer, 21, 423 (1980), diazonium salt, US Pat. No. 4,0
69,055, JP-A-4-365049, etc., phosphonium salts described in US Pat. Nos. 4,069,055 and 4,069,056, European patents Nos. 104 and 143, U.S. Pat. Nos. 339,049 and 410,201, JP-A-2-150848 and JP-A-2-296514, iodonium salts, European Patent 370, 693, 390,214, 233,567, 297,443, 297,442, U.S. Pat.Nos. 4,933,377, 161,811, 410,201, 339,049, 4,760,
No. 013, No. 4,734,444, No. 2,833,827, German Patent No. 2,90
Sulfonium salts described in the specifications of U.S. Pat. Nos. 4,626, 3,604,580 and 3,604,581; V. Crivello et al, Macromolecule
s, 10 (6), 1307 (1977), J. MoI. V. Crivello et al, J.A.
Polymer Sci. , Polymer Chem. Ed. , 17, 1047 (19
79), selenonium salts according to C. S. Wen et al, Teh, Proc. Co
nf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), and onium salts such as arsonium salts.

In the present invention, these onium salts function not as acid generators but as ionic radical polymerization initiators.
The onium salts preferably used in the present invention are represented by the following general formulas (RI-I) to (RI-II).
An onium salt represented by I).

In the formula (RI-I), Ar ₁₁ represents an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents, and preferred substituents include an alkyl group having 12 or less carbon atoms and 12 carbon atoms. The following alkenyl groups, alkynyl groups having 12 or less carbon atoms, aryl groups having 12 or less carbon atoms, alkoxy groups having 12 or less carbon atoms, aryloxy groups having 12 or less carbon atoms, halogen atoms, alkylamino groups having 12 or less carbon atoms, carbon A dialkylamino group having 12 or less carbon atoms, an alkylamide group or arylamide group having 12 or less carbon atoms, a carbonyl group, a carboxyl group, a cyano group, a sulfonyl group, a thioalkyl group having 12 or less carbon atoms, and a thioaryl group having 12 or less carbon atoms. It is done. Z ₁₁ ^- represents a monovalent anion, specifically a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, a sulfate ion Can be mentioned. Of these, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion and sulfinate ion are preferable from the viewpoint of stability.

In the formula (RI-II), Ar ₂₁ and Ar ₂₂ each independently represent an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents, and preferred substituents are 12 or less carbon atoms. Alkyl group, alkenyl group having 12 or less carbon atoms, alkynyl group having 12 or less carbon atoms, aryl group having 12 or less carbon atoms, alkoxy group having 12 or less carbon atoms, aryloxy group having 12 or less carbon atoms, halogen atom, 12 carbon atoms The following alkylamino group, dialkylamino group having 12 or less carbon atoms, alkylamide group or arylamide group having 12 or less carbon atoms, carbonyl group, carboxyl group, cyano group, sulfonyl group, thioalkyl group having 12 or less carbon atoms, carbon number Examples include 12 or less thioaryl groups. Z ₂₁ ^- represents a monovalent anion. Specific examples include halogen ions, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonate ions, sulfinate ions, thiosulfonate ions, and sulfate ions. Among these, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, and carboxylate ion are preferable from the viewpoint of stability and reactivity.

In the formula (RI-III), R ₃₁ , R ₃₂ and R ₃₃ are each independently an aryl group, alkyl group, alkenyl group or alkynyl having 20 or less carbon atoms, which may have 1 to 6 substituents. Represents a group. Among them, an aryl group is preferable from the viewpoint of reactivity and stability. Examples of the substituent include an alkyl group having 12 or less carbon atoms, an alkenyl group having 12 or less carbon atoms, an alkynyl group having 12 or less carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 12 or less carbon atoms, and 12 or less carbon atoms. Aryloxy group, halogen atom, alkylamino group having 12 or less carbon atoms, dialkylamino group having 12 or less carbon atoms, alkylamide group or arylamide group having 12 or less carbon atoms, carbonyl group, carboxyl group, cyano group, sulfonyl group, Examples thereof include a thioalkyl group having 12 or less carbon atoms and a thioaryl group having 12 or less carbon atoms. Z ₃₁ ^- represents a monovalent anion. Specific examples include halogen ions, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonate ions, sulfinate ions, thiosulfonate ions, and sulfate ions. Of these, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, and carboxylate ion are preferable from the viewpoints of stability and reactivity. More preferred are the carboxylate ions described in JP-A No. 2001-343742, and particularly preferred are the carboxylate ions described in JP-A No. 2002-148790.

The polymerization initiator is not limited to the above, but particularly from the viewpoint of reactivity and stability, a triazine-based initiator, an organic halogen compound, a metallocene compound, a hexaarylbiimidazole compound,
More preferred are oxime ester compounds, diazonium salts, iodonium salts, and sulfonium salts.

Only 1 type may be used for a polymerization initiator and it may use 2 or more types together. Further, the polymerization initiator may be added to the same layer as other components, or another layer may be provided and added thereto. The polymerization initiator is preferably added in an amount of 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and particularly preferably 0.8 to 20% by mass with respect to the total solid content constituting the photosensitive layer. can do.

(Binder polymer)
As the binder polymer that can be used in the photosensitive layer of the present invention, a water-insoluble polymer is preferably used. Furthermore, the binder polymer that can be used in the present invention preferably contains substantially no acid group such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group, and the acid value of the binder polymer (the acid content per gram of the polymer). Chemical equivalence number) is 0.3 meq
/ G or less, more preferably 0.1 meq / g or less.
That is, the binder polymer that can be used in the present invention is preferably insoluble in water and an aqueous solution having a pH of 10 or more, and the solubility of the binder polymer in water and an aqueous solution having a pH of 10 or more is 0.5% by mass or less. Preferably, more preferably 0.1
It is below mass%. By using such a binder polymer, the film strength, water resistance and fillability of the photosensitive layer are improved, and the printing durability is improved.

As the binder polymer, as long as the performance of the lithographic printing plate precursor according to the invention is not impaired, a conventionally known one can be used without limitation within the above-mentioned characteristic range, and a linear organic polymer having a film property is preferable.
As an example of such a binder polymer, a polymer selected from acrylic resins, polyvinyl acetal resins, polyurethane resins, polyamide resins, epoxy resins, methacrylic resins, styrene resins, and polyester resins is preferable. Especially, an acrylic resin is preferable and a (meth) acrylic acid ester copolymer is preferable. More specifically, (meth) acrylic acid alkyl or aralkyl ester and (meth) acrylic acid ester residue (
To R of the -COOR) contains a -CH ₂ CH ₂ O- unit or a -CH ₂ CH ₂ NH- unit (meth)
A copolymer with an acrylate ester is particularly preferred. The preferable alkyl group of the said (meth) acrylic-acid alkylester is a C1-C5 alkyl group, and a methyl group is more preferable. Preferable (meth) acrylic acid aralkyl esters include benzyl (meth) acrylate.

Further, the binder polymer can be cross-linked in order to improve the film strength of the image area.
In order to give the binder polymer crosslinkability, a crosslinkable functional group may be introduced into the main chain or side chain of the polymer. The crosslinkable functional group may be introduced by copolymerization or may be introduced by a polymer reaction.

Here, the crosslinkable functional group is a group that crosslinks the binder polymer in the process of radical polymerization reaction that occurs in the photosensitive layer when the lithographic printing plate precursor is exposed. Although it will not specifically limit if it is a group of such a function, For example, an ethylenically unsaturated bond group, an amino group, an epoxy group etc. are mentioned as a functional group which can be addition-polymerized. Moreover, the functional group which can become a radical by light irradiation may be sufficient, As such a crosslinkable functional group, a thiol group, a halogen group, an onium salt structure etc. are mentioned, for example. Especially, an ethylenically unsaturated bond group is preferable and the functional group represented by the following general formula (1)-(3) is especially preferable.

In the general formula (1), R ^{1 to} R ³ each independently represent a hydrogen atom or a monovalent organic group. R ¹ preferably includes a hydrogen atom or an alkyl group which may have a substituent. Among them, a hydrogen atom or a methyl group is more preferable because of high radical reactivity. R ² and R ³ are each independently a hydrogen atom, a halogen atom, an amino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an optionally substituted alkyl group, or a substituent. An aryl group that may have a substituent, an alkoxy group that may have a substituent, an aryloxy group that may have a substituent, an alkylamino group that may have a substituent, and a substituent Arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, and the like. Among them, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, a substituent may be mentioned. An alkyl group which may have a substituent and an aryl group which may have a substituent are more preferable because of high radical reactivity.

X represents an oxygen atom, a sulfur atom, or —N (R ¹² ) —, and R ¹² represents a hydrogen atom or 1
Represents a valent organic group. Examples of the monovalent organic group include an alkyl group which may have a substituent. R ¹² is preferably a hydrogen atom, a methyl group, an ethyl group, or an isopropyl group because of high radical reactivity.

Here, examples of the substituent that can be introduced include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a halogen atom, an amino group, an alkylamino group,
Arylamino group, carboxyl group, alkoxycarbonyl group, sulfo group, nitro group, cyano group, amide group, alkylsulfonyl group, arylsulfonyl group and the like can be mentioned.

In the general formula (2), R ^{4 to} R ⁸ each independently represent a hydrogen atom or a monovalent organic group. R ^{4 to} R ⁸ are preferably a hydrogen atom, a halogen atom, an amino group, a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, or an alkyl group which may have a substituent. An aryl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylamino group which may have a substituent, An arylamino group which may have, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, etc. are mentioned, among them, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, An alkyl group which may have a substituent and an aryl group which may have a substituent are more preferable.

Examples of the substituent that can be introduced are the same as those in the general formula (1).
Y represents an oxygen atom, a sulfur atom, or —N (R ¹² ) —. R ¹² is R in the general formula (1)
^It is synonymous with ¹² , and a preferable example is also the same.

In the general formula (3), R ^{9 to} R ¹¹ each independently represents a hydrogen atom or a monovalent organic group. Examples of the monovalent organic group include an alkyl group which may have a substituent. R ⁹ is preferably a hydrogen atom or a methyl group because of high radical reactivity. R ¹⁰ ,
R ¹¹ is preferably independently a hydrogen atom, a halogen atom, an amino group, a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, or an alkyl which may have a substituent. Group, aryl group which may have a substituent, alkoxy group which may have a substituent, aryloxy group which may have a substituent, alkylamino group which may have a substituent, substituent An arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, etc., among them, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group An alkyl group which may have a substituent and an aryl group which may have a substituent are more preferable because of high radical reactivity.

Here, examples of the substituent that can be introduced are the same as those in the general formula (1). Further, Z is an oxygen atom, a sulfur atom, -N (R ¹³⁾ -, or a phenylene group which may have a substituent. Examples of R ¹³ include an alkyl group which may have a substituent.
Of these, a methyl group, an ethyl group, and an isopropyl group are preferable because of high radical reactivity.
Among these, (meth) acrylic acid copolymers having a crosslinkable group in the side chain and polyurethane are more preferable.

For example, the binder polymer having a crosslinkable property has a free radical (
A polymerization initiating radical or a growth radical in the polymerization process of the polymerizable compound) is added, and addition polymerization is performed directly between polymers or via a polymerization chain of the polymerizable compound, and a crosslink is formed between the polymer molecules to be cured. Alternatively, atoms in the polymer (for example, hydrogen atoms on carbon atoms adjacent to the crosslinkable functional group) are extracted by free radicals to form polymer radicals that are bonded to each other, thereby causing crosslinking between polymer molecules. Forms and cures.

The content of the crosslinkable functional group in the binder polymer (content of the unsaturated double bond capable of radical polymerization by iodine titration) is preferably 0.1 per gram of the hydrophobic binder polymer.
-10.0 mmol, more preferably 1.0-7.0 mmol, most preferably 2.0-
5.5 mmol.

Further, it is preferable that the binder polymer is hydrophilic from the viewpoint of improving developability with respect to an aqueous solution, and it is important that the binder polymer is compatible with the polymerizable compound contained in the photosensitive layer from the viewpoint of improving printing durability. Yes, ie lipophilic. From such a viewpoint, in the present invention, it is also effective to copolymerize a hydrophilic group and an oleophilic group in the binder polymer in order to improve developability and printing durability. Examples of the hydrophilic group include a hydroxy group, a carboxylate group, a hydroxyethyl group, an ethyleneoxy group, a hydroxypropyl group, a polyoxyethyl group, a polyoxypropyl group, an amino group, an aminoethyl group, an aminopropyl group, and an ammonium group. And amide group, carboxymethyl group, sulfonate group, phosphonate group and the like.

The binder polymer preferably has a mass average molecular weight of 5,000 or more and 10,000 to 3
More preferably, the number average molecular weight is 1,000 or more.
More preferably, it is 2000-250,000. Polydispersity (mass average molecular weight / number average molecular weight)
Is preferably 1.1-10.
The binder polymer may be any of a random polymer, a block polymer, a graft polymer, and the like, but is preferably a random polymer.

A binder polymer may be used independently or may be used in mixture of 2 or more types.
The content of the binder polymer is 5 to 90% by mass with respect to the total solid content of the photosensitive layer,
It is preferably 10 to 70% by mass, and more preferably 10 to 60% by mass. Within this range, good image area strength and image formability can be obtained.

(Sensitizing dye)
The photosensitive layer preferably contains a sensitizing dye corresponding to the wavelength of the exposure light source. The sensitizing dye is appropriately selected according to the use to be used and is not particularly limited.
Examples thereof include a sensitizing dye that absorbs light of 350 nm to 450 nm, an infrared absorber, and the like.
<Sensitizing dye that absorbs light of 350 nm to 450 nm>
The sensitizing dye that absorbs light of 350 nm to 450 nm used in the present invention preferably has an absorption maximum in a wavelength region of 350 nm to 450 nm. Examples of such a sensitizing dye include merocyanine dyes represented by the following general formula (I), benzopyrans and coumarins represented by the following general formula (II), and fragrances represented by the following general formula (III). And anthracenes represented by the following general formula (IV).

(In the formula, A represents an S atom or NR ₆ , R ₆ represents a monovalent non-metallic atomic group, Y represents a basic nucleus of a dye in cooperation with an adjacent A and an adjacent carbon atom. metallic atomic group, X1, X ₂ each independently represents a monovalent non-metallic atomic group, X _1, X ₂ may be bonded to form an acidic nucleus of the dye together.)

(In the formula, = Z represents an oxo group, a thioxo group, an imino group or an alkylidene group represented by the partial structural formula (I ′), and X ₁ and X ₂ have the same meaning as in the general formula (II); R _{7 to} R ₁₂ each independently represents a monovalent nonmetallic atomic group.)

(In the formula, Ar ₃ represents an aromatic group or a heteroaromatic group which may have a substituent, and R _1
3 represents a monovalent nonmetallic atomic group. R ₁₃ is more preferably an aromatic group or a heteroaromatic group, and Ar ₃ and R ₁₃ may be bonded to each other to form a ring. )

(In the formula, X ₃ , X ₄ and R _{14 to} R ₂₁ each independently represent a monovalent non-metallic atomic group, and more preferable X ₃ and X ₄ are electron donating groups having a negative Hammett's substituent constant. .)

Preferred examples of the monovalent nonmetallic atomic group represented by X ₁ to X ₄ and R ₆ to R ₂₁ in the general formulas (I) to (IV) include a hydrogen atom, an alkyl group (for example, a methyl group, Ethyl group,
Propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group,
Decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group, octadecyl group, eicosyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group A 2-ethylhexyl group,
2-methylhexyl, cyclohexyl, cyclopentyl, 2-norbornyl, chloromethyl, bromomethyl, 2-chloroethyl, trifluoromethyl, methoxymethyl, methoxyethoxyethyl, allyloxymethyl, phenoxymethyl Group, methylthiomethyl group, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N-
Cyclohexylcarbamoyloxyethyl group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxycarbonylethyl group, allyloxycarbonyl Butyl group, chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (
Methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) carbamoylmethyl group, sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoyl Propyl group, N-tolylsulfamoylpropyl group, N-methyl-N- (phosphonophenyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group,
Diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group, tolylphosphonohexyl group, tolylphosphonatohexyl group, phosphonooxypropyl group, phosphonatoxybutyl group, benzyl group, phenethyl group, α- Methylbenzyl group, 1-methyl-1-phenylethyl group, p-methylbenzyl group, cinnamyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl group, 2 -Propynyl group, 2-butynyl group, 3-butynyl group, etc.),

Aryl groups (for example, phenyl, biphenyl, naphthyl, tolyl, xylyl,
Mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthio Phenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, nitrophenyl group, cyanophenyl Group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl group, phosphonatophenyl group, etc.), heteroaryl group (for example,
Thiophene, thiathrene, furan, pyran, isobenzofuran, chromene, xanthene,
Phenoxazine, pyrrole, pyrazole, isothiazole, isoxazole, pyrazine, pyrimidine, pyridazine, indolizine, isoindolizine, indoyl, indazole, purine, quinolidine, isoquinoline, phthalazine, naphthyridine, quinazoline, cinolin, pteridine, carbazole, carboline , A group derived from a heteroaryl ring such as phenanthrin, acridine, perimidine, phenanthroline, phthalazine, phenazazine, phenoxazine, furazane, phenoxazine, etc., an alkenyl group (for example, vinyl group, 1-propenyl group, 1-butenyl group) Cinnamyl group, 2-chloro-1-ethenyl group, etc.),
Alkynyl group (for example, ethynyl group, 1-propynyl group, 1-butynyl group, trimethylsilylethynyl group, etc.), halogen atom (—F, —Br, —Cl, —I), hydroxyl group, alkoxy group, aryloxy group,

Mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio 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, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N'-alkylureido group, N ' , N′-dialkylureido group, N′-arylureido group, N ′, '- diaryl ureido group, N'- alkyl -N'- arylureido group, N- alkylureido group, N- arylureido group, N'- alkyl -N-
Alkylureido group, N′-alkyl-N-arylureido group, N ′, N′-dialkyl-N—
Alkylureido group, N ′, N′-dialkyl-N-arylureido group, N′-aryl-N
-Alkylureido group, N'-aryl-N-arylureido group, N ', N'-diaryl-N-
Alkylureido group, N ′, N′-diaryl-N-arylureido group, N′-alkyl-N
'-Aryl-N-alkylureido group, N'-alkyl-N'-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N
-Alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N
-Aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N , N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group ( -SO ₃ H) and its conjugate base group (hereinafter referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group,

N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, phosphono Group (—PO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as phosphonate group), dialkylphosphono group (—PO ₃ (alkyl
₂ ), diaryl phosphono group (—PO ₃ (aryl) ₂ ), alkyl aryl phosphono group (—P
O ₃ (alkyl) (aryl)), monoalkyl phosphono group (—PO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkyl phosphonate group), monoaryl phosphono group (—PO ₃ H (a
ryl)) and its conjugate base group (hereinafter referred to as arylphosphonate group), phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as phosphonatooxy group), dialkylphosphonooxy Group (-OPO ₃ (alkyl) ₂ ), diarylphosphonooxy group (-
OPO ₃ (aryl) ₂ ), an alkylarylphosphonooxy group (—OPO ₃ (alkyl) (aryl)),
A monoalkylphosphonooxy group (—OPO ₃ H (alkyl)) and its conjugate base group (hereinafter,
Alkylphosphonateoxy group), monoarylphosphonooxy group (-OPO ₃ H
(aryl)) and conjugated base groups thereof (hereinafter referred to as arylphosphonatooxy groups), cyano groups, nitro groups, and the like. Among these groups, a hydrogen atom, an alkyl group, an aryl group, a halogen atom, An alkoxy group and an acyl group are particularly preferable.

Examples of the basic nucleus of the dye formed together with A adjacent to Y in the general formula (I) and the adjacent carbon atom include 5-, 6-, and 7-membered nitrogen-containing or sulfur-containing heterocycles, A 5- or 6-membered heterocyclic ring is preferable.

Examples of nitrogen-containing heterocycles include, for example, LGBrooker et al., J. Am. Chem. Soc., 73,532
Any of those known to constitute a basic nucleus in merocyanine dyes described in 6-5358 (1951). And references can be suitably used. Specific examples include thiazoles (for example, thiazole, 4-methylthiazole, 4-phenylthiazole, 5-
Methylthiazole, 5-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole, 4,5-di (p-methoxyphenylthiazole), 4- (2-thienyl)
Thiazole, etc.), benzothiazoles (eg, benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 4-phenylbenzothiazole, 5-phenylbenzothiazole, 4-methoxybenzothiazole, 5-methoxybenzothiazole,
6-methoxybenzothiazole, 5-iodobenzothiazole, 6-iodobenzothiazole, 4-ethoxybenzothiazole, 5-ethoxybenzothiazole, tetrahydrobenzothiazole, 5,6-dimethoxybenzothiazole, 5,6-dioxymethylenebenzo Thiazole, 5-hydroxybenzothiazole, 6-hydroxybenzothiazole, 6-dimethylaminobenzothiazole, 5-ethoxycarbonylbenzothiazole, etc.), naphthothiazoles (for example, naphtho [1,2] thiazole, naphtho [2,1] Thiazole, 5-methoxynaphtho [2,1] thiazole, 5-ethoxynaphtho [2,1] thiazole, 8-methoxynaphtho [1,2] thiazole, 7-methoxynaphtho [1,2] thiazole, etc.), thianaphtheno- 7 ', 6', 4,5-thiazole (E.g., 4'-methoxy Chiana Fute Bruno -7 '
, 6 ′, 4,5-thiazole, etc.), oxazoles (for example, 4-methyloxazole, 5
-Methyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole, 4-
Ethyl oxazole, 4,5-dimethyloxazole, 5-phenyloxazole, etc.), benzoxazoles (benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-phenylbenzoxazole, 6-methylbenzoxazole, 5
, 6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, 6-methoxybenzoxazole, 5-methoxybenzoxazole, 4-ethoxybenzoxazole, 5-chlorobenzoxazole, 6-methoxybenzoxazole, 5-hydroxybenzoxazole , 6-hydroxybenzoxazole, etc.), naphthoxazoles (eg, naphtho [1,2] oxazole, naphtho [2,1] oxazole, etc.), selenazoles (eg, 4-methylselenazole, 4-phenylselenazole, etc.) ), Benzoselenazoles (eg, benzoselenazole, 5-chlorobenzoselenazole, 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole, tetrahydrobenzoselenazole, etc.), naphthoselenazoles (eg, Shift [1,2] selenazole, naphtho [2,1]
Selenazole, etc.), thiazolines (eg, thiazoline, 4-methylthiazoline, etc.), quinolines (eg, quinoline, 3-methylquinoline, 5-methylquinoline, 7-methylquinoline, 8-methylquinoline, 6-chloroquinoline, 8-chloroquinoline, 6-methoxyquinoline, 6-ethoxyquinoline, 6-hydroxyquinoline, 8-hydroxyquinoline, etc.), isoquinolines (eg, isoquinoline, 3,4-dihydroisoquinoline, etc.), benzimidazoles (eg, 1 , 3-diethylbenzimidazole, 1-ethyl-3-phenylbenzimidazole, etc.), 3,3-dialkylindolenins (for example, 3,3-dimethylindolenin, 3,3,5-trimethylindolenine, 3 , 3,7, -trimethylindolenine, etc.), pyridines (eg, pyridine, - it can be exemplified methyl pyridine) and the like.

Examples of the sulfur-containing heterocycle include a dithiol partial structure in dyes described in JP-A-3-296759.
Specific examples include benzodithiols (for example, benzodithiol, 5-t-butylbenzodithiol, 5-methylbenzodithiol, etc.), naphthodithiols (for example, naphtho [
1,2] dithiol, naphtho [2,1] dithiol, etc.), dithiols (for example, 4,5
-Dimethyldithiols, 4-phenyldithiols, 4-methoxycarbonyldithiols, 4,5-dimethoxycarbonyldithiols, 4,5-ditrifluoromethyldithiol, 4,5-dicyanodithiol, 4-methoxycarbonylmethyldithiol, 4-Carboxymethyldithiol and the like can be mentioned.

As mentioned above, the description used for the description of the heterocyclic ring described above has conventionally used the name of the heterocyclic mother skeleton for convenience, but in the case of the basic skeleton partial structure of the sensitizing dye, for example, in the case of the benzothiazole skeleton , 3-substituted-2 (3H) -benzothiazolylidene groups, such as alkylidene type substituents with one degree of unsaturation.

Among sensitizing dyes as compounds having an absorption maximum in the wavelength region of 350 nm to 450 nm,
A dye more preferable from the viewpoint of high sensitivity is a dye represented by the following general formula (V).

(In the general formula (V), A represents an aromatic ring or a hetero ring which may have a substituent, and X represents an oxygen atom, a sulfur atom or ═N (R ₃ ). R ₁ , R ₂ and R ₃ each independently represents a monovalent nonmetallic atomic group, and A and R ₁ or R ₂ and R ₃ may be bonded to each other to form an aliphatic or aromatic ring. .)

The general formula (V) will be described in more detail. R ₁ , R ₂ and R ₃ are each independently
Monovalent non-metal atomic group, preferably substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted aryl group, substituted or unsubstituted heteroaryl group, substituted or unsubstituted Represents an alkoxy group, a substituted or unsubstituted alkylthio group, a hydroxyl group, and a halogen atom.

Preferable examples of R ₁ , R ₂ and R ₃ will be specifically described. Examples of preferable alkyl groups include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, Butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, s-butyl, t-butyl group, isopentyl group, neopentyl group, 1
-Methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group, 2-norbornyl group. Of these, linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, and cyclic alkyl groups having 5 to 10 carbon atoms are more preferable.

As the substituent of the substituted alkyl group, a monovalent nonmetallic atomic group excluding hydrogen is used, and preferred examples include halogen atoms (—F, —Br, —Cl, —I), hydroxyl groups, alkoxy groups, Aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio 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-dialkyl Carbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group, acylthio group, acylamino group, N-alkylacylamino group, N-aryl Acylamino group, ureido group, N′-alkylureido group, N ′,
N'-dialkylureido group, N'-arylureido group, N ', N'-diarylureido group, N'-alkyl-N'-arylureido group, N-alkylureido group, N-arylureido group, N' -Alkyl-N-alkylureido groups, N'-alkyl-N-arylureido groups,
N ′, N′-dialkyl-N-alkylureido group, N ′, N′-dialkyl-N-arylureido group, N′-aryl-N-alkylureido group, N′-aryl-N-arylureido group, N
', N'-diaryl-N-alkylureido group, N', N'-diaryl-N-arylureido group, N'-alkyl-N'-aryl-N-alkylureido group, N'-alkyl-N ' -Aryl-
N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group N-aryl-N-aryloxycarbonylamino group, acyl group, carboxyl group, alkoxycarbonyl group,

Aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, alkylsulfinyl group, Arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (—SO ₃ H) and its conjugate base group (hereinafter referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkyls Rufinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkyl Sulfamoyl group, N, N-dia Kill sulfamoyl group, N- aryl sulfamoyl group, N, N- diaryl sulfamoyl group, N- alkyl -N- arylsulfamoyl group,
Phosphono group (—PO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as “phosphonate group”), dialkyl phosphono group (—PO ₃ (alkyl) ₂ ), diaryl phosphono group (—PO ₃ (aryl) ₂ )
, An alkylaryl phosphono group (—PO ₃ (alkyl) (aryl)), a monoalkyl phosphono group (—PO ₃ H (alkyl)) and a conjugate base group thereof (hereinafter referred to as an alkyl phosphonate group),
Monoaryl phosphono group (—PO ₃ H (aryl)) and its conjugate base group (hereinafter referred to as aryl phosphonate group), phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as phosphine group) Onatooxy group), dialkylphosphonooxy group (-OPO ₃ (alkyl) ₂
), Diaryl phosphonooxy group (—OPO ₃ (aryl) ₂ ), alkylaryl phosphonooxy group (—OPO ₃ (alkyl) (aryl)), monoalkyl phosphonooxy group (—OPO ₃ H (al
kyl)) and its conjugate base group (hereinafter referred to as alkylphosphonatooxy group), monoarylphosphonooxy group (—OPO ₃ H (aryl)) and its conjugate base group (hereinafter referred to as arylphosphonatooxy group) ), A cyano group, a nitro group, an aryl group, a heteroaryl group, an alkenyl group, and an alkynyl group.

Specific examples of the alkyl group in these substituents include the above-described alkyl groups, and specific examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, a mesityl group, and a cumenyl group. , Chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylamino Phenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group,
Examples thereof include an ethoxyphenylcarbonyl group, a phenoxycarbonylphenyl group, an N-phenylcarbamoylphenyl group, a phenyl group, a cyanophenyl group, a sulfophenyl group, a sulfonatophenyl group, a phosphonophenyl group, and a phosphonatophenyl group.

As the heteroaryl group, a monocyclic ring containing at least one of nitrogen, oxygen and sulfur atoms,
Alternatively, a polycyclic aromatic ring group is used, and examples of particularly preferred heteroaryl groups include, for example, thiophene, thiathrene, furan, pyran, isobenzofuran, chromene, xanthene, phenoxazine, pyrrole, pyrazole, isothiazole, isoxazole. , Pyrazine, pyrimidine, pyridazine, indolizine, isoindolizine, indoir, indazole, purine, quinolidine, isoquinoline, phthalazine, naphthyridine, quinazoline, cinnoline, pteridine, carbazole, carboline, phenanthrin, acridine, perimidine, phenanthroline, phthalazine Groups derived from heteroaryl rings such as phenalzazine, phenoxazine, furazane, phenoxazine, etc., and these may be further benzo-fused, Substituent may have.

Examples of alkenyl groups include vinyl, 1-propenyl, 1-butenyl, cinnamyl, 2-chloro-1-ethenyl, etc. Examples of alkynyl include ethynyl, 1-propynyl Group, 1-butynyl group, trimethylsilylethynyl group and the like. Examples of G ₁ in the acyl group (G ₁ CO—) include hydrogen and the above alkyl groups and aryl groups. Of these substituents, halogen atoms (—F, —Br, —Cl, —I), alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, N-alkylamino groups, N, N— Dialkylamino group, acyloxy group, N-
Alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group,
Formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group , Sulfo group,
Sulfonato group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group, phosphonato group, Dialkyl phosphono group, diaryl phosphono group, monoalkyl phosphono group, alkyl phosphonate group, monoaryl phosphono group,
Examples thereof include an aryl phosphonate group, a phosphonooxy group, a phosphonate oxy group, an aryl group, and an alkenyl group.

On the other hand, examples of the alkylene group in the substituted alkyl group include a divalent organic residue obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. Can include linear alkylene groups having 1 to 12 carbon atoms, branched chains having 3 to 12 carbon atoms, and cyclic alkylene groups having 5 to 10 carbon atoms.

Specific examples of preferred substituted alkyl groups as R ₁ , R ₂ and R ₃ obtained by combining the above substituents with an alkylene group include chloromethyl group, bromomethyl group, 2-chloroethyl group, trifluoromethyl group, methoxymethyl Group, methoxyethoxyethyl group,
Allyloxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl group, N -Phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxycarbonylethyl group, allyloxycarbonylbutyl group, chlorophenoxycarbonylmethyl Group, carbamoylmethyl group, N-methylcarbamoylethyl group,
N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) carbamoylmethyl group, sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfuryl group Famoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N-methyl-
N- (phosphonophenyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group, tolylphosphono Hexyl group, tolylphosphonatohexyl group, phosphonooxypropyl group, phosphonatooxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p-methylbenzyl group, cinnamyl Group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, and the like.

Specific examples of preferred aryl groups as R ₁ , R ₂ and R ₃ include those in which 1 to 3 benzene rings form a condensed ring, and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. Specific examples include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group. Among these, a phenyl group and a naphthyl group are more preferable.

Specific examples of preferred substituted aryl groups as R ₁ , R _2, and R ₃ include those having a monovalent non-metallic atomic group excluding hydrogen as a substituent on the ring-forming carbon atom of the aforementioned aryl group. . Examples of preferred substituents include the aforementioned alkyl groups, substituted alkyl groups, and
The thing previously shown as a substituent in a substituted alkyl group can be mentioned. Like this,
Preferred examples of the substituted aryl group include biphenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, fluorophenyl group, chloromethylphenyl group, trifluoromethylphenyl group, hydroxyphenyl group. , Methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, benzoyloxyphenyl group N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, carboxyphenyl group Methoxycarbonylphenyl group, allyloxycarbonyl phenyl group, chlorophenoxy carbonyl phenyl group, carbamoyl phenyl group, N-
Methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group, N-methyl-N-sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoyl Phenyl group, N
-Ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group, N-
Tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenylphosphonophenyl group, methylphosphonophenyl Group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonophenyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallylphenyl group, 2-methylpropenylphenyl group, 2- Examples include propynylphenyl group, 2-butynylphenyl group, and 3-butynylphenyl group.

Specific examples of preferred substituted or unsubstituted alkenyl groups and substituted or unsubstituted heteroaryl groups as R ₁ , R ₂ and R ₃ are the same as those described above for alkenyl groups and heteroaryl groups. be able to.

Next, A in the general formula (V) will be described. A represents an aromatic ring group or a heterocyclic group which may have a substituent, and specific examples of the aromatic ring group and the heterocyclic group which may have a substituent include those in the general formula (V) Examples are the same as the aryl group and heteroaryl group described for R ₁ , R ₂ and R ₃ .

The sensitizing dye represented by the general formula (V) is obtained by a condensation reaction between an acidic nucleus having an acidic nucleus or an active methylene group as shown above and a substituted or unsubstituted aromatic ring or heterocyclic ring. It is done. Specifically, it can be synthesized with reference to the description of JP-B-59-28329.

Preferred specific examples (D1) to (D41) of the compound represented by the general formula (V) are shown below. In addition, the isomer by the double bond connecting the acidic nucleus and the basic nucleus is not limited to either isomer.

The sensitizing dye having an absorption maximum in the wavelength range of 350 nm to 450 nm is preferably used in a range of 1.0 to 10.0% by mass with respect to the total solid content of the photosensitive layer. More preferably 1
. It is in the range of 5 to 8.0% by mass.

<Infrared absorber>
An infrared absorber is a component used to increase sensitivity to an infrared laser.
The infrared absorber has a function of converting absorbed infrared rays into heat. The infrared absorber preferably used in the present invention is a dye or pigment having an absorption maximum at a wavelength of 760 to 1200 nm.

Examples of the dye include commercially available dyes and, for example, “Dye Handbook” (edited by the Society of Synthetic Organic Chemistry, Showa 45).
The publicly known ones described in documents such as “Annual” can be used. Specifically, dyes such as 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, etc. Is mentioned.

Preferred dyes include, for example, JP-A-58-125246 and JP-A-59-8435.
6, cyanine dyes described in JP-A-60-78787, etc., JP-A-58-173
No. 696, JP-A 58-181690, JP-A 58-194595, etc., methine dyes, 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., and naphthoquinone dyes described in JP-A-58-112792, etc. Examples include squarylium pigments and cyanine dyes described in British Patent No. 434,875.

Further, a near infrared absorption sensitizer described in US Pat. No. 5,156,938 is also preferably used, and a substituted arylbenzo (thio) described in US Pat. No. 3,881,924 is also preferred. ) Pyrylium salt, trimethine thiapyrylium salt described in JP-A-57-142645 (US Pat. No. 4,327,169), JP-A-58-181051, and 58-2
20143, 59-41363, 59-84248, 59-84249,
Pyryllium compounds described in JP-A-59-146063 and JP-A-59-146061, cyanine dyes described in JP-A-59-216146, US Pat. No. 4,283,4
No. 75, pentamethine thiopyrylium salt, etc., and Japanese Patent Publication No. 5-13514, 5
A pyrylium compound disclosed in JP-A-19702 is also preferably used. In addition, as another preferred example of the dye, U.S. Pat. No. 4,756,993 has the formula (I), (
Mention may be made of the near-infrared absorbing dyes described as II).

Moreover, as another preferable example of the infrared absorbing dye, JP-A-20
Specific indolenine cyanine dyes described in JP-A-02-278057.

Particularly preferred among these dyes are cyanine dyes, squarylium dyes,
Examples include pyrylium salts, nickel thiolate complexes, and indolenine cyanine dyes. Further, cyanine dyes and indolenine cyanine dyes are preferred, and one particularly preferred example is a cyanine dye represented by the following general formula (I).

In the general formula (I), 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, a nitrogen 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 1 carbon atom containing a hetero atom.
-12 hydrocarbon groups are shown. Here, the hetero atom means N, S, O, halogen atom,
Se is shown. Xa ^- the Za described later ^- is synonymous with, R ^a represents a hydrogen atom, an alkyl group, 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 photosensitive 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. Preferred substituents include hydrocarbon groups having 12 or less carbon atoms,
Examples thereof include a halogen atom and an alkoxy group having 12 or less carbon atoms. 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 (I) has an anionic substituent in its structure and neutralization of charge 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 hexafluoro ion, in view of the storage stability of the photosensitive layer coating solution. Phosphate ion and aryl sulfonate ion.

Specific examples of the cyanine dye represented by formula (I) that can be suitably used in the present invention include paragraph numbers [0017] to [0019] of JP-A No. 2001-133969.
] Can be mentioned.

Further, other particularly preferable examples include specific indolenine cyanine dyes described in JP-A-2002-278057 described above.

Examples of the pigment used in the present invention include commercially available pigments and color indexes (C.I.
. ) Handbook, “Latest Pigment Handbook” (edited by the Japan Pigment Technology Association, published in 1977), “Latest Pigment Applied Technology” (published by CMC, 1986), “Printing Ink Technology”, published by CMC, published in 1984) Is available.

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 ,
Loso pigments, nitro pigments, natural materials, 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” (Yokoshobo), “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 to 10 μm, more preferably in the range of 0.05 to 1 μm, and particularly preferably in the range of 0.1 to 1 μm. Within this range, good stability and uniformity of the pigment dispersion in the photosensitive layer can be obtained.

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).

  These infrared absorbers can be added by being encapsulated in microcapsules.

As the addition amount, it is preferable to add so that the absorbance at the maximum absorption wavelength in the wavelength range of 760 nm to 1200 nm of the photosensitive layer is in the range of 0.3 to 1.3 by the reflection measurement method, more preferably, It is in the range of 0.4 to 1.2. Within this range, a uniform polymerization reaction proceeds in the depth direction of the photosensitive layer, and good film strength of the image area and adhesion to the support can be obtained.
The absorbance of the photosensitive layer can be adjusted by the amount of infrared absorber added to the photosensitive layer and the thickness of the photosensitive layer. Absorbance can be measured by a conventional method. For example, on a reflective support such as aluminum, a photosensitive layer having a thickness that is appropriately determined within a range where the coating amount after drying is necessary for a lithographic printing plate precursor is formed, and the reflection density is measured with an optical densitometer. And a method of measuring with a spectrophotometer by a reflection method using an integrating sphere.

(Co-sensitizer)
The sensitivity of the photosensitive layer can be further improved by using certain additives. Such a compound is referred to as a co-sensitizer in the present invention. These mechanisms of action are not clear, but many are thought to be based on the following chemical processes. That is, the photoreaction initiated by light absorption of the above-described photopolymerization initiation system and various intermediate active species (radicals, peroxides, oxidizing agents, reducing agents, etc.) generated in the course of the subsequent addition polymerization reaction, It is presumed that the sensitizer reacts to generate a new active radical. The co-sensitizers are roughly classified into (a) those that can be reduced to generate active radicals, (b) those that can be oxidized to generate active radicals, and (c) more active by reacting with less active radicals. However, there are many cases where there is no general rule as to which individual compounds belong to them.

(A) Compound that is reduced to produce an active radical Compound having a carbon-halogen bond: It is considered that an active radical is generated by reductive cleavage of the carbon-halogen bond. Specifically, for example, trihalomethyl-s-triazines and trihalomethyloxadiazoles can be preferably used.
Compound having nitrogen-nitrogen bond: It is considered that the nitrogen-nitrogen bond is reductively cleaved to generate an active radical. Specifically, hexaarylbiimidazoles and the like are preferably used.
Compound having oxygen-oxygen bond: It is considered that the oxygen-oxygen bond is reductively cleaved to generate an active radical. Specifically, for example, organic peroxides are preferably used.
Onium compounds: It is considered that carbon-hetero bonds and oxygen-nitrogen bonds are reductively cleaved to generate active radicals. Specifically, for example, diaryliodonium salts, triarylsulfonium salts, N-alkoxypyridinium (azinium) salts and the like are preferably used.
Ferrocene and iron arene complexes: An active radical can be reductively generated.

(B) Compound which is oxidized to generate an active radical Alkylate complex: It is considered that a carbon-hetero bond is oxidatively cleaved to generate an active radical. Specifically, for example, triarylalkyl borates are preferably used.
Alkylamine compound: It is considered that the C—X bond on carbon adjacent to nitrogen is cleaved by oxidation to generate an active radical. X is preferably a hydrogen atom, a carboxyl group, a trimethylsilyl group, a benzyl group or the like. Specifically, for example, ethanolamines,
N-phenylglycine, N-trimethylsilylmethylaniline, etc. are mentioned.
Sulfur-containing and tin-containing compounds: Compounds in which the nitrogen atoms of the above-described amines are replaced with sulfur atoms and tin atoms can generate active radicals by the same action. A compound having an S—S bond is also S.
Sensitization due to -S cleavage is known.

α-Substituted methylcarbonyl compound: An active radical can be generated by oxidative cleavage of the carbonyl-α carbon bond. Moreover, what converted carbonyl into the oxime ether also shows the same effect | action. Specifically, 2-alkyl-1- [4- (alkylthio) phenyl]
Examples include -2-morpholinopronone-1 and oxime ethers obtained by reacting these with hydroxyamines and then etherifying N-OH.
Sulfinic acid salts: An active radical can be reductively generated. Specific examples include sodium arylsulfinate.

(C) Compounds that react with radicals to convert to highly active radicals or act as chain transfer agents Compounds that react with radicals to convert to highly active radicals or act as chain transfer agents include, for example, SH, PH in the molecule , SiH, and GeH are used.
These can donate hydrogen to low-activity radical species to generate radicals, or can be oxidized and then deprotonated to generate radicals. Specifically, for example, 2-
And mercaptobenzimidazoles.

More specific examples of these co-sensitizers are disclosed in, for example, JP-A-9-236913.
Many are described as additives for the purpose of improving sensitivity. Some examples are shown below, but the present invention is not limited thereto.

These co-sensitizers can also be subjected to various chemical modifications for improving the characteristics of the photosensitive layer of the lithographic printing plate precursor as in the case of the sensitizing dye. For example, sensitizing dyes, polymerization initiators, polymerizable compounds, bonding with other radical generating parts, introduction of hydrophilic sites, improved compatibility, introduction of substituents to suppress crystal precipitation, substituents that improve adhesion Methods such as introduction and polymerization can be used. These co-sensitizers can be used alone or in combination of two or more. The amount used is 0.05 to 100 parts by mass, preferably 1 to 80 parts by mass, and more preferably 3 to 50 parts by mass with respect to 100 parts by mass of the polymerizable compound.

(Microcapsule)
In the present invention, examples of methods for incorporating the above-described photosensitive layer constituents and other constituents described later into the photosensitive layer include, for example, JP-A Nos. 2001-277740 and 2001-27.
As described in Japanese Patent No. 7742, a part of the components can be encapsulated in microcapsules and added to the photosensitive layer. In that case, each component can be contained in any ratio in and out of the microcapsule.

As a method for microencapsulating the photosensitive layer constituent components, known methods can be applied. For example, as a method for producing microcapsules, U.S. Pat.
No. 458, method utilizing coacervation, US Pat. No. 3,287,715
Method of interfacial polymerization found in each specification of No. 4, Japanese Patent Publication Nos. 38-19574 and 42-446, and precipitation of polymers found in US Pat. Nos. 3,418,250 and 3,660,304 A method using an isocyanate polyol wall material found in US Pat. No. 3,796,669, a method using an isocyanate wall material found in US Pat. No. 3,914,511, US Pat. Nos. 4,001,140, 4,087,376,
US Pat. No. 4,089,802, a method using a urea-formaldehyde-based or urea-formaldehyde-resorcinol-based wall forming material, a wall material such as melamine-formaldehyde resin, hydroxycellulose, etc., as disclosed in US Pat. No. 4,025,445. Method used, in situ method by monomer polymerization as seen in JP-Bs 36-9163 and 51-9079, British Patent No. 930422, US Pat. No. 3,111,407, Spray drying method, British Patent Examples thereof include, but are not limited to, the electrolytic dispersion cooling method and the like found in the specifications of Nos. 952807 and 967074.

A preferable microcapsule wall used in the present invention has a three-dimensional cross-linking and has a property of swelling with a solvent. From such a viewpoint, the wall material of the microcapsule is preferably polyurea, polyurethane, polyester, polycarbonate, polyamide, and a mixture thereof, and particularly preferably polyurea and polyurethane. Moreover, you may introduce | transduce into the microcapsule wall the compound which has crosslinkable functional groups, such as an ethylenically unsaturated bond which can be introduce | transduced into said water-insoluble polymer.

The average particle size of the microcapsules is preferably 0.01 to 3.0 μm. 0.05 ~
2.0 μm is more preferable, and 0.10 to 1.0 μm is particularly preferable. Within this range, good resolution and stability over time can be obtained.

(Surfactant)
In the present invention, it is preferable to use a surfactant in the photosensitive layer in order to promote developability and improve the coated surface state. Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and fluorosurfactants.

The nonionic surfactant used for this invention is not specifically limited, A conventionally well-known thing can be used. For example, 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, polyglycerin fatty acid partial esters, polyoxyethylenated castor oil , Polyoxyethylene glycerin fatty acid partial esters, fatty acid diethanolamides, N, N-bis-2-hydroxyalkylamines, polyoxyethylene alkylamine, triethanolamine fatty acid ester, trialkylamine oxide, polyethylene glycol, polyethylene And a copolymer of glycol and polypropylene glycol.

The anionic surfactant used in the present invention is not particularly limited, and conventionally known anionic surfactants can be used. For example, fatty acid salts, abietic acid salts, hydroxyalkane sulfonates, alkane sulfonates, dialkyl sulfosuccinate esters, linear alkyl benzene sulfonates, branched alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl phenoxy poly Oxyethylene propyl sulfonates, polyoxyethylene alkyl sulfophenyl ether salts, N-methyl-N-oleyl taurine sodium salt, N-alkyl sulfosuccinic acid monoamide disodium salt, petroleum sulfonates, sulfated beef oil, fatty acid alkyl esters Sulfates, alkyl sulfates, polyoxyethylene alkyl ether sulfates, fatty acid monoglyceride sulfates, polyoxyethylene alcohol Ruphenyl ether sulfates, polyoxyethylene styryl phenyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates, styrene / maleic anhydride Examples thereof include partial saponification products of polymers, partial saponification products of olefin / maleic anhydride copolymers, and naphthalene sulfonate formalin condensates.

The cationic surfactant used in the present invention is not particularly limited, and conventionally known cationic surfactants can be used. Examples thereof include alkylamine salts, quaternary ammonium salts, polyoxyethylene alkylamine salts, and polyethylene polyamine derivatives.
The amphoteric surfactant used in the present invention is not particularly limited, and conventionally known amphoteric surfactants can be used. Examples thereof include carboxybetaines, aminocarboxylic acids, sulfobetaines, aminosulfuric acid esters, and imidazolines.

Of the above surfactants, the term “polyoxyethylene” can be read as “polyoxyalkylene” such as polyoxymethylene, polyoxypropylene, polyoxybutylene, etc. These surfactants can also be used.

More preferable surfactants include fluorine-based surfactants containing a perfluoroalkyl group in the molecule. Examples of such fluorosurfactants include anionic types such as perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, and perfluoroalkyl phosphates; amphoteric types such as perfluoroalkyl betaines; Cation type such as trimethylammonium salt; perfluoroalkylamine oxide, perfluoroalkylethylene oxide adduct, oligomer containing perfluoroalkyl group and hydrophilic group, oligomer containing perfluoroalkyl group and lipophilic group, perfluoroalkyl Nonionic types such as an oligomer containing a group, a hydrophilic group and a lipophilic group, and a urethane containing a perfluoroalkyl group and a lipophilic group. JP-A-62-170950, JP-A-62-226143, and JP-A-60-168144.
Fluorosurfactant described in the publication of No. is also preferably mentioned.

Surfactant can be used individually or in combination of 2 or more types.
The content of the surfactant is preferably 0.001 to 10% by mass and more preferably 0.01 to 7% by mass with respect to the total solid content of the photosensitive layer.

(Hydrophilic polymer)
In the present invention, for improving developability, improving dispersion stability of microcapsules, etc.,
A hydrophilic polymer can be contained in the photosensitive layer. Examples of hydrophilic polymers include:
Hydroxy group, carboxyl group, carboxylate group, hydroxyethyl group, polyoxyethyl group, hydroxypropyl group, polyoxypropyl group, amino group, aminoethyl group,
Preferable examples include those having hydrophilic groups such as aminopropyl group, ammonium group, amide group, carboxymethyl group, sulfonic acid group, and phosphoric acid group.

Specific examples include gum arabic, casein, gelatin, starch derivatives, carboxymethylcellulose and its sodium salt, cellulose acetate, sodium alginate,
Vinyl acetate-maleic acid copolymers, styrene-maleic acid copolymers, polyacrylic acids and their salts, polymethacrylic acids and their salts, homopolymers and copolymers of hydroxyethyl methacrylate, homopolymers and copolymers of hydroxyethyl acrylate, hydroxy Homopolymers and copolymers of pyropyrmethacrylate, homopolymers and copolymers of hydroxypropyl acrylate, homopolymers and copolymers of hydroxybutyl methacrylate, homopolymers and copolymers of hydroxybutyl acrylate, polyethylene glycols, hydroxypropylene polymers, polyvinyl alcohols, water Decomposition degree is 60 mol% or more, preferably 80 mol%
Hydrolyzed polyvinyl acetate, polyvinyl formal, polyvinyl butyral, polyvinyl pyrrolidone, homopolymers and copolymers of acrylamide, homopolymers and polymers of methacrylamide, homopolymers and copolymers of N-methylol acrylamide, polyvinyl pyrrolidone, alcohol soluble nylon, 2 , 2-bis-
And polyether of (4-hydroxyphenyl) -propane and epichlorohydrin.

The hydrophilic polymer preferably has a mass average molecular weight of 5000 or more, more preferably 10,000 to 300,000. The hydrophilic polymer may be any of a random polymer, a block polymer, a graft polymer, and the like.
The content of the hydrophilic polymer in the photosensitive layer is preferably 20% by mass or less based on the total solid content of the photosensitive layer,
10 mass% or less is more preferable.

(Coloring agent)
In the present invention, a dye having a large absorption in the visible light region can be used as an image colorant. Specifically, oil yellow # 101, oil yellow # 103, oil pink #
312, Oil Green BG, Oil Blue BOS, Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-505 (orientated chemical industry (
Co., Ltd.), Victoria Pure Blue, Crystal Violet (CI42555), Methyl Violet (CI42535), Ethyl Violet, Rhodamine B (CI4517)
0B), malachite green (CI42000), methylene blue (CI52015) and the like, and dyes described in JP-A-62-293247.
Also, pigments such as phthalocyanine pigments, azo pigments, carbon black, titanium oxide, etc. can be suitably used.

These colorants are preferably added since it is easy to distinguish an image area from a non-image area after image formation. The addition amount is preferably 0.01 to 10% by mass with respect to the total solid content of the photosensitive layer.

(Bake-out agent)
In the photosensitive layer of the present invention, a compound that changes color by an acid or a radical can be added in order to form a printout image. As such a compound, for example, diphenylmethane,
Triphenylmethane, thiazine, oxazine, xanthene, anthraquinone,
Various dyes such as iminoquinone, azo, and azomethine are effectively used.

Specific examples include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsin, methyl violet 2B, quinaldine red, rose bengal, methanyl yellow, thymol sulfophthalein, xylenol blue, methyl orange, paramethyl red, Congo Fred, Benzopurpurin 4B, α-
Naphthyl Red, Nile Blue 2B, Nile Blue A, Methyl Violet, Malachite Green, Parafuchsin, Victoria Pure Blue BOH [Hodogaya Chemical Co., Ltd.], Oil Blue # 603 [Orient Chemical Industries Co., Ltd.], Oil Pink # 312 [Orient Chemical Industries, Ltd.], Oil Red 5B [Orient Chemical Industries, Ltd.], Oil Scarlet # 308 [Orient Chemical Industries, Ltd.], Oil Red OG [Orient Chemical Industries, Ltd.], Oil Red RR [Orient Chemical Co., Ltd.], Oil Green #
502 [made by Orient Chemical Industry Co., Ltd.], Spiron Red BEH Special [made by Hodogaya Chemical Co., Ltd.], m-cresol purple, cresol red, rhodamine B, rhodamine 6G, sulforhodamine B, auramin, 4-p-diethylaminophenyl Iminonaphthoquinone, 2-carboxyanilino-4-p-diethylaminophenyliminonaphthoquinone, 2-carboxystearylamino-4-pN, N-bis (hydroxyethyl) amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl Dyes such as -4-p-diethylaminophenylimino-5-pyrazolone and 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone, and p, p ′, p ″ -hexamethyltriaminotriphenylmethane ( Leuco crystal And leuco dyes such as Pergascript Blue SRB (manufactured by Ciba Geigy).

In addition to the above, a leuco dye known as a material for thermal paper or pressure-sensitive paper is also suitable. Specific examples include crystal violet lactone, malachite green lactone, benzoyl leucomethylene blue, 2- (N-phenyl-N-methylamino).
-6- (Np-tolyl-N-ethyl) amino-fluorane, 2-anilino-3-methyl-6- (N-ethyl-p-toluidino) fluorane, 3,6-dimethoxyfluorane, 3
-(N, N-diethylamino) -5-methyl-7- (N, N-dibenzylamino) -fluorane, 3- (N-cyclohexyl-N-methylamino) -6-methyl-7-anilinofluorane 3- (N, N-diethylamino) -6-methyl-7-anilinofluorane, 3
-(N, N-diethylamino) -6-methyl-7-xylidinofluorane, 3- (N, N
-Diethylamino) -6-methyl-7-chlorofluorane, 3- (N, N-diethylamino) -6-methoxy-7-aminofluorane, 3- (N, N-diethylamino) -7- (
4-chloroanilino) fluorane, 3- (N, N-diethylamino) -7-chlorofluorane, 3- (N, N-diethylamino) -7-benzylaminofluorane, 3- (N, N
-Diethylamino) -7,8-benzofluorane, 3- (N, N-dibutylamino) -6
-Methyl-7-anilinofluorane, 3- (N, N-dibutylamino) -6-methyl-7
-Xylidinofluorane, 3-piperidino-6-methyl-7-anilinofluorane, 3-
Pyrrolidino-6-methyl-7-anilinofluorane, 3,3-bis (1-ethyl-2-methylindol-3-yl) phthalide, 3,3-bis (1-n-butyl-2-methylindole) -3-yl) phthalide, 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-
And ethyl-2-methylindol-3-yl) -4-zaphthalide, 3- (4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) phthalide, and the like.

A suitable addition amount of the dye that changes color by an acid or radical is 0.
It is a ratio of 01 to 15% by mass.

(Polymerization inhibitor)
It is preferable to add a small amount of a thermal polymerization inhibitor to the photosensitive layer of the present invention in order to prevent unnecessary thermal polymerization of the polymerizable compound during the production or storage of the photosensitive layer.
Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-
Butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4
'-Thiobis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4
-Methyl-6-t-butylphenol) and N-nitroso-N-phenylhydroxylamine aluminum salts are preferred.
The addition amount of the thermal polymerization inhibitor is preferably about 0.01 to about 5% by mass with respect to the total solid content of the photosensitive layer.

(Higher fatty acid derivatives)
In order to prevent polymerization inhibition by oxygen, a higher fatty acid derivative such as behenic acid or behenamide is added to the photosensitive layer of the present invention so that it is unevenly distributed on the surface of the photosensitive layer during the drying process after coating. May be. The addition amount of the higher fatty acid derivative is about 0.1 to about 1 with respect to the total solid content of the photosensitive layer.
It is preferably 0% by mass.

(Plasticizer)
The photosensitive layer of the present invention may contain a plasticizer. Examples of the plasticizer include phthalates such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, octyl capryl phthalate, dicyclohexyl phthalate, ditridecyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, diallyl phthalate; Glycol esters such as glycol phthalate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, triethylene glycol dicaprylate; Phosphate esters such as tricresyl phosphate and triphenyl phosphate Diisobutyl adipate;
Aliphatic dibasic acid esters such as dioctyl adipate, dimethyl sebacate, dibutyl sebacate, dioctyl azelate, dibutyl maleate; polyglycidyl methacrylate, triethyl citrate, glycerin triacetyl ester, butyl laurate and the like are preferable. . The plasticizer content is preferably about 30% by mass or less based on the total solid content of the photosensitive layer.

(Inorganic fine particles)
The photosensitive layer of the present invention may contain inorganic fine particles in order to improve the strength of the cured film in the image area. As the inorganic fine particles, for example, silica, alumina, magnesium oxide, titanium oxide, magnesium carbonate, calcium alginate, or a mixture thereof is preferably exemplified. Even if they are not photothermally convertible, they can be used for strengthening the film, enhancing interfacial adhesion by surface roughening, and the like. The inorganic fine particles preferably have an average particle size of 5 nm to 10 μm,
More preferably, it is ˜3 μm. Within the above range, it is possible to form a non-image portion having excellent hydrophilicity, which is stably dispersed in the photosensitive layer, sufficiently retains the film strength of the photosensitive layer, and hardly causes stains during printing.
The inorganic fine particles as described above can be easily obtained as a commercial product such as a colloidal silica dispersion.
The content of the inorganic fine particles is preferably 20% by mass or less, and more preferably 10% by mass or less, based on the total solid content of the photosensitive layer.

(Hydrophilic low molecular weight compound)
The photosensitive layer of the present invention can contain a hydrophilic low molecular weight compound for improving developability.
Examples of hydrophilic low molecular weight compounds include water-soluble organic compounds such as glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, and tripropylene glycol, and ether or ester derivatives thereof, glycerin, Polyhydroxys such as pentaerythritol, organic amines such as triethanolamine and diethanolamine monoethanolamine and salts thereof,
Organic sulfonic acids such as toluenesulfonic acid and benzenesulfonic acid and their salts, organic phosphonic acids such as phenylphosphonic acid and their salts, organic carboxylic acids such as tartaric acid, oxalic acid, citric acid, malic acid, lactic acid, gluconic acid, amino acids Examples thereof include acids and salts thereof, and organic quaternary ammonium salts such as tetraethylamine hydrochloride.

(Formation of photosensitive layer)
The photosensitive layer of the present invention is formed by preparing or applying a coating solution by dispersing or dissolving the necessary components described above in a solvent. Solvents used here 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, dimethoxy Examples include ethane, methyl lactate, ethyl lactate, N, N-dimethylacetamide, N, N-dimethylformamide, tetramethylurea, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, γ-butyllactone, toluene, water, and the like. However, the present invention is not limited to this. These solvents are used alone or in combination. The solid content concentration of the coating solution is preferably 1 to 50% by mass.
The photosensitive layer of the present invention can be formed by preparing a plurality of coating solutions in which the same or different components are dispersed or dissolved in the same or different solvents, and repeatedly applying and drying a plurality of times.

The photosensitive layer coating amount (solid content) on the support obtained after coating and drying varies depending on the use, but is generally preferably 0.3 to 3.0 g / m ² . Within this range, good sensitivity and good film properties of the photosensitive layer can be obtained.
Various methods can be used as a coating method. Examples thereof include bar coater coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating, and roll coating.

[Protective layer]
In the lithographic printing plate precursor according to the invention, a protective layer (oxygen blocking layer) is preferably provided on the photosensitive layer in order to block diffusion and penetration of oxygen that hinders the polymerization reaction during exposure. The protective layer used in the present invention has an oxygen permeability A of 1.0 ≦ A ≦ 20 (mL / m ² · day) at 25 ° C. and 1 atm.
) Is preferable. When the oxygen permeability A is extremely low at less than 1.0 (mL / m ² · day), unnecessary polymerization reaction occurs at the time of production and raw storage, and unnecessary fogging and image streaking occur during image exposure. The problem that fatness arises arises. Conversely, oxygen permeability A is 20 (mL / m
If it exceeds ² · day) and is too high, the sensitivity is lowered. The oxygen permeability A is more preferably 1.5 ≦ A ≦ 12 (mL / m ² · day), and further preferably 2.0 ≦ A ≦ 10.0 (m
L / m ² · day). In addition to the oxygen permeability described above, the properties desired for the protective layer further do not substantially inhibit the transmission of light used for exposure, have excellent adhesion to the photosensitive layer, and are easy in the development process after exposure. It can be removed. The device concerning such a protective layer has been conventionally made, and is described in detail in US Pat. No. 3,458,311 and JP-B-55-49729.

As a material for the protective layer, for example, a water-soluble polymer compound having relatively excellent crystallinity is preferably used. Specifically, polyvinyl alcohol, vinyl alcohol / vinyl phthalate copolymer, vinyl acetate / vinyl alcohol / Water-soluble polymers such as vinyl phthalate copolymer, vinyl acetate / crotonic acid copolymer, polyvinyl pyrrolidone, acidic celluloses, gelatin, gum arabic, polyacrylic acid, polyacrylamide, etc., may be used alone or in combination Can be used. Of these, the use of polyvinyl alcohol as the main component gives the best results in terms of basic properties such as oxygen barrier properties and development removability.

The polyvinyl alcohol used for the protective layer may be partially substituted with an ester, an ether, and an acetal as long as it contains an unsubstituted vinyl alcohol unit for having necessary oxygen barrier properties and water solubility. Similarly, some of them may have other copolymer components. Specific examples of the polyvinyl alcohol include those having a hydrolysis degree of 71 to 100 mol% and a polymerization repeating unit of 300 to 2400. Specifically, Kuraray Co., Ltd. PVA-105, PVA-110, PVA-117, PVA-117H, PV
A-120, PVA-124, PVA-124H, PVA-CS, PVA-CST, PV
A-HC, PVA-203, PVA-204, PVA-205, PVA-210, PVA
-217, PVA-220, PVA-224, PVA-217EE, PVA-217E,
PVA-220E, PVA-224E, PVA-405, PVA-420, PVA-61
3, L-8 and the like, and these can be used alone or in combination. As a preferred embodiment, the content of polyvinyl alcohol in the protective layer is 20 to 95% by mass, more preferably 30%.
It is -90 mass%.

Moreover, well-known modified polyvinyl alcohol can also be used preferably. For example, various hydrophilic modification sites such as anion modification sites modified with anions such as carboxyl groups and sulfo groups, cation modification sites modified with cations such as amino groups and ammonium groups, silanol modification sites, and thiol modification sites are randomly selected. Polyvinyl alcohol having various degrees of polymerization, the anion-modified site, the cation-modified site, the silanol-modified site, the thiol-modified site, the alkoxyl-modified site, the sulfide-modified site, and the ester modification of vinyl alcohol and various organic acids. Examples thereof include polyvinyl alcohol having various polymerization degrees having various modified sites such as a site, an ester-modified site of the anion-modified site and alcohols, an epoxy-modified site, and the like.

As a component used by mixing with polyvinyl alcohol, polyvinyl pyrrolidone or a modified product thereof is preferable from the viewpoints of oxygen barrier properties and development removability, and the content in the protective layer is 3.
It is 5-80 mass%, Preferably it is 10-60 mass%, More preferably, it is 15-30 mass%.

Components of the protective layer (selection of PVA, use of additives), coating amount, and the like are selected in consideration of anti-fogging properties, adhesion, and scratch resistance in addition to oxygen barrier properties and development removability. In general, the higher the hydrolysis rate of the PVA used (the higher the content of the unsubstituted vinyl alcohol unit in the protective layer), the higher the film thickness, the higher the oxygen barrier property and the more advantageous in terms of sensitivity. Polyvinyl alcohol (PVA)
The molecular weight of the polymer compound such as) can be in the range of 2000 to 10 million, preferably in the range of 20,000 to 3 million.

As another composition of the protective layer, glycerin, dipropylene glycol and the like can be added in an amount corresponding to several mass% with respect to the polymer compound to give flexibility, and also sodium alkyl sulfate, sodium alkyl sulfonate Anionic surfactants such as; amphoteric surfactants such as alkylaminocarboxylates and alkylaminodicarboxylates; nonionic surfactants such as polyoxyethylene alkylphenyl ethers are added in several mass% relative to the polymer compound be able to.

In addition, adhesion to the image area and scratch resistance are extremely important in handling the plate. That is, when a hydrophilic layer made of a water-soluble polymer is laminated on a lipophilic photosensitive layer, film peeling due to insufficient adhesion tends to occur, and the peeled part causes defects such as poor film hardening due to inhibition of oxygen polymerization. On the other hand, various proposals have been made to improve the adhesion between these two layers. For example, in U.S. Patent Application No. 292,501 and U.S. Patent Application No. 44,563, an acrylic emulsion or a water-insoluble vinyl pyrrolidone-vinyl acetate copolymer is contained in a hydrophilic polymer mainly composed of polyvinyl alcohol. It is described that sufficient adhesiveness can be obtained by mixing 20 to 60% by mass and laminating on a photosensitive layer. Any of these known techniques can be applied to the protective layer in the present invention. As for the method of coating such a protective layer, for example, US Pat. No. 3,458,311 and JP-B-5
This is described in detail in Japanese Patent No. 5-49729.

Furthermore, the protective layer in the lithographic printing plate precursor according to the invention preferably contains an inorganic stratiform compound for the purpose of improving oxygen barrier properties and photosensitive layer surface protection.
Here, the inorganic layered compound is a particle having a thin flat plate shape, for example, a general formula: A (B, C) _2-5 D ₄ O ₁₀ (OH, F, O) ₂ [where A Is any of K, Na, and Ca, B and C are any of Fe (II), Fe (III), Mn, Al, Mg, and V, and D is Si or Al. And mica groups such as natural mica and synthetic mica represented by the following general formula: talc, teniolite, montmorillonite, saponite, hectorite, zirconium phosphate represented by the general formula: 3MgO.4SiO.H ₂ O.

In the mica group, natural mica includes muscovite, soda mica, phlogopite, biotite, and sericite. As the synthetic mica, fluorine phlogopite KMg ₃ (AlSi ₃ O ₁₀
) F ₂ , Potassium tetrasilicon mica KMg _2.5 Si ₄ O ₁₀ ) Non-swelling mica such as F ₂ , and Na tetrasilicic mica NaMg _2.5 (Si ₄ O ₁₀ ) F ₂ , Na or Li teniolite (Na
, Li) Mg ₂ Li (Si ₄ O ₁₀ ) F ₂ , montmorillonite-based Na or Li hectorite (Na, Li) _1/8 Mg _{2 /} 5Li _1/8 (Si ₄ O ₁₀ ) F _2, etc. Sexual mica etc. are mentioned. Synthetic smectite is also useful.

In the present invention, among the inorganic layered compounds, fluorine-based swellable mica, which is a synthetic inorganic layered compound, is particularly useful. That is, this swelling synthetic mica and swellable viscosity minerals such as montmorillonite, saponite, hectorite, bentonite, etc.
It has a laminated structure composed of unit crystal lattice layers with a thickness of about ˜15 mm, and the substitution of metal atoms in the lattice is significantly larger than other viscosity minerals. As a result, the lattice layer is deficient in positive charges, and cations such as Na ⁺ , Ca ²⁺ and Mg ²⁺ are adsorbed between the layers in order to compensate for this. The cations present between these layers are called exchangeable cations and exchange with various cations. In particular, when the cation between the layers is Li ⁺ or Na ⁺ , the bond between the layered crystal lattices is weak because the ionic radius is small, and the layer swells greatly with water. If shear is applied in this state, it will easily cleave and form a stable sol in water. Bentonite and swellable synthetic mica have this tendency and are useful in the present invention, and swellable synthetic mica is particularly preferably used.

As the shape of the inorganic layered compound used in the present invention, from the viewpoint of diffusion control, the smaller the thickness, the better. The plane size is as long as it does not hinder the smoothness of the coated surface or the transmittance of actinic rays. Larger is better. Therefore, the aspect ratio is 20 or more, preferably 100
Above, particularly preferably 200 or more. The aspect ratio is the ratio of the thickness to the major axis of the particle, and can be measured, for example, from a projected view of the particle by a micrograph. The larger the aspect ratio, the greater the effect that can be obtained.

  As for the particle diameter of the inorganic stratiform compound used in the present invention, the average major axis is 0.3 to 20 μm, preferably 0.5 to 10 μm, particularly preferably 1 to 5 μm. The average thickness of the particles is 0.1 μm or less, preferably 0.05 μm or less, particularly preferably 0.01 μm or less. For example, among inorganic layered compounds, the size of the swellable synthetic mica that is a representative compound is about 1 to 50 nm in thickness and about 1 to 20 μm in surface size.

When particles of inorganic layered compounds having a large aspect ratio are contained in the protective layer,
The coating film strength is improved and the permeation of oxygen and moisture can be effectively prevented, preventing deterioration of the protective layer due to deformation, etc., even if stored for a long time under high humidity conditions, due to changes in humidity It is excellent in storage stability without deterioration of image formability in a lithographic printing plate precursor.

The content of the inorganic stratiform compound in the protective layer is relative to the amount of binder used in the protective layer.
The mass ratio is preferably 5/1 to 1/100. Even when a plurality of inorganic layered compounds are used in combination, the total amount of these inorganic layered compounds is preferably the above-described mass ratio.

  Next, an example of a general dispersion method of the inorganic layered compound used for the protective layer will be described. First, 5 to 10 parts by mass of the swellable layered compound mentioned above as a preferred inorganic layered compound is added to 100 parts by mass of water, and the mixture is thoroughly swelled and swollen, and then dispersed by a disperser. Examples of the disperser used here include various mills that disperse mechanically by applying a direct force, a high-speed stirring disperser having a large shearing force, and a disperser that provides high-intensity ultrasonic energy. Specifically, ball mill, sand grinder mill, visco mill, colloid mill, homogenizer, tisol bar, polytron, homomixer, homo blender, ketdy mill, jet agitator, capillary emulsifier, liquid siren, electrostrictive ultrasonic generator, An emulsifying device having a Paulman whistle can be used. A dispersion of 5 to 10% by mass of the inorganic layered compound dispersed by the above method is highly viscous or gelled, and has very good storage stability. When preparing a protective layer coating solution using this dispersion, it is preferably prepared by diluting with water and stirring sufficiently, and then blending with a binder solution.

  In addition to the inorganic layered compound, known additives such as a surfactant for improving coatability and a water-soluble plasticizer for improving the physical properties of the film can be added to the protective layer coating solution. . Examples of the water-soluble plasticizer include propionamide, cyclohexanediol, glycerin, sorbitol and the like. A water-soluble (meth) acrylic polymer can also be added. Furthermore, known additives for improving the adhesion to the photosensitive layer and the temporal stability of the coating solution may be added to the coating solution.

The protective layer coating solution thus prepared is applied onto the photosensitive layer and dried to form a protective layer. The coating solvent can be appropriately selected in relation to the binder, but when a water-soluble polymer is used, it is preferable to use distilled water or purified water. The method for applying the protective layer is not particularly limited, and is described in US Pat. No. 3,458,311 or JP-B-55-
Known methods such as the method described in Japanese Patent No. 49729 can be applied. Specific examples of the protective layer include blade coating, air knife coating, gravure coating, roll coating coating, spray coating, dip coating, and bar coating.

The coating amount of the protective layer is preferably in the range of 0.05 to 10 g / m ^{2 in} terms of the coating amount after drying. When the inorganic layered compound is contained, 0.1 to 0.5 g / More preferably in the range of m ² , 0.5 to 5 g when no inorganic layered compound is contained.
More preferably, it is in the range of / m ² .

[Back coat layer]
If necessary, a back coat can be provided on the back surface of the support. Examples of the back coat include hydrolysis and polycondensation of an organic polymer compound described in JP-A-5-45885, an organometallic compound or an inorganic metal compound described in JP-A-6-35174. A coating layer made of a metal oxide obtained in this way is preferred. Among them, it is inexpensive to use a silicon alkoxy compound such as Si (OCH ₃ ) ₄ , Si (OC ₂ H ₅ ) ₄ , Si (OC ₃ H ₇ ) ₄ , Si (OC ₄ H ₉ ) _4. It is preferable in terms of easy availability.

Next, the heat fusion type lithographic printing plate precursor will be described.
<Heat-fusion type image forming layer>
The image forming layer in the heat fusion type lithographic printing plate precursor may contain heat fusible fine particles, and the heat fusible fine particles may have a fused form, that is, a latex film structure.

  As the heat-fusible fine particles used in the present invention, heat-fusible polymer fine particles are suitable.

  Specific examples of polymers that form such fine particles include homopolymers obtained from monomers such as ethylene, styrene, vinyl chloride, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, vinylidene chloride, acrylonitrile, vinyl carbazole and the like. Or a copolymer or a mixture thereof. Among these, more preferred are polystyrene and methyl polymethacrylate.

  These fine particles can be produced by an emulsion polymerization method, a suspension polymerization method, a method in which a polymer is dissolved in an organic solvent and emulsified and dispersed in water, and then the solvent is evaporated (solvent evaporation method), or a mechanical dispersion method.

  As the heat-fusible polymer for forming the heat-fusible fine particles used in the present invention, a polymer having a functional group (heat-reactive group) that reacts with heat can also be used. A polymer having a thermoreactive group is more preferable from the viewpoint of forming a firm image.

  Examples of the thermally reactive group include an ethylenically unsaturated group that undergoes a polymerization reaction (for example, acryloyl group, methacryloyl group, vinyl group, and allyl group), an isocyanate group that undergoes an addition reaction, or a block thereof, and a reaction partner thereof. A functional group having an active hydrogen atom (for example, an amino group, a hydroxyl group, a carboxyl group, etc.), an epoxy group that performs an addition reaction, and an amino group, a carboxyl group, or a hydroxyl group that is a reaction partner, a carboxyl group that performs a condensation reaction And a hydroxyl group or an amino group, an acid anhydride that performs a ring-opening addition reaction, an amino group, or a hydroxyl group. However, as long as a chemical bond is formed by heat fusion, any functional group that performs any reaction may be used.

  The introduction of these heat-reactive groups into the polymer particles may be performed during the polymerization of the fine particle polymer, or may be performed using a polymer reaction after the polymerization of the fine particle polymer.

  When introduced during the polymerization of the fine particle polymer, it is preferable to carry out emulsion polymerization or suspension polymerization of the monomer having these heat-reactive groups. Specific examples of the monomer having such a functional group include allyl methacrylate, allyl acrylate, vinyl methacrylate, vinyl acrylate, glycidyl methacrylate, glycidyl acrylate, 2-isocyanate ethyl methacrylate, or block isocyanates based on alcohols thereof, 2-isocyanate ethyl acrylate. Or block isocyanates with alcohols, 2-aminoethyl methacrylate, 2-aminoethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, acrylic acid, methacrylic acid, maleic anhydride, bifunctional acrylate, bifunctional methacrylate However, it is not limited to these.

  In the case of introducing a monomer having these heat-reactive groups during polymerization, a monomer having no heat-reactive group can be copolymerized with the monomer having the heat-reactive group. Examples of such a monomer having no copolymerizable heat-reactive group include styrene, alkyl acrylate, alkyl methacrylate, acrylonitrile, vinyl acetate, etc., but the monomer does not have a heat-reactive group. If it is, it will not be limited to these.

  Examples of the polymer reaction used in the case where the introduction of the thermally reactive group is performed after the polymer fine particles are polymerized include the polymer reaction described in WO96-34316.

  The weight average molecular weight of the polymer fine particles not having the heat-reactive group and the polymer fine particles having the heat-reactive group described above is suitably in the range of 2,000 to 1,000,000.

  The average particle diameter of the polymer fine particles is preferably from 0.01 to 20 μm, more preferably from 0.03 to 1.00 μm, particularly preferably from 0.05 to 0.40 μm, from the viewpoint of achieving both image formability and developability. preferable.

  It is preferable from the viewpoint of image formation that these polymer fine particles contain a photothermal conversion agent because the thermal efficiency during exposure is good. Such fine particles containing a photothermal conversion agent can be obtained by dissolving the photothermal conversion agent together when the polymer is dissolved in a water-insoluble organic solvent by the solvent evaporation method.

  A hydrophilic resin can be added to the image forming layer of the heat fusion type lithographic printing plate precursor according to the invention. By adding a hydrophilic resin, not only the developability to an aqueous solution having a pH of 2 to 10 is improved, but also the film strength of the image forming layer itself is increased. As the hydrophilic resin, those not three-dimensionally crosslinked are preferable because of good developability.

  As hydrophilic resin, what has hydrophilic groups, such as a hydroxyl group, a carboxyl group, a hydroxyethyl group, a hydroxypropyl group, an amino group, an aminoethyl group, an aminopropyl group, a carboxymethyl group, for example is preferable.

  Specific examples of hydrophilic resins include gum arabic, casein, gelatin, starch derivatives, soya gum, hydroxypropylcellulose, methylcellulose, carboxymethylcellulose and its salts, cellulose acetate, sodium alginate, vinyl acetate-maleic acid copolymers, styrene-maleic acid Copolymers, polyacrylic acids and salts thereof, polymethacrylic acids and salts thereof, homopolymers and copolymers of hydroxyethyl methacrylate, homopolymers and copolymers of hydroxyethyl acrylate, homopolymers and copolymers of hydroxypropyl methacrylate, hydroxypropyl acrylate Homopolymers and copolymers, hydroxybutyl methacrylate homopolymers and copolymers, Roxybutyl acrylate homopolymers and copolymers, polyethylene glycols, hydroxypropylene polymers, polyvinyl alcohols, and hydrolyzed polyvinyl acetate having a degree of hydrolysis of at least 60% by weight, preferably at least 80% by weight, polyvinyl formal, polyvinyl butyral, Examples thereof include polyvinylpyrrolidone, homopolymers and copolymers of acrylamide, homopolymers and polymers of methacrylamide, homopolymers and copolymers of N-methylolacrylamide, 2-acrylamido-2-methylpropanesulfonic acid and salts thereof.

  The amount of the hydrophilic resin added to the image forming layer is preferably from 2 to 40% by weight, more preferably from 3 to 30% by weight, based on the solid content of the image forming layer, from the viewpoint of good developability and high printing durability.

  In addition to the resin fine particles and the hydrophilic resin, the image forming layer of the heat fusion type lithographic printing plate precursor according to the present invention has improved sensitivity, control of the degree of hydrophilicity, improvement of physical strength of the image forming layer, layer The composition comprising a photothermal conversion agent that absorbs light and generates heat for various purposes such as improvement of mutual dispersibility, improvement of coatability, improvement of printability, and convenience of plate making workability, inorganic fine particles, surfactant Various compounds such as a colorant and a plasticizer can be added as necessary. These will be described below.

  The photothermal conversion agent may be any substance that absorbs light of 700 nm or more, and various pigments, dyes, metal fine particles, and the like can be used. Specific examples of the photothermal conversion agent include the infrared absorbers described for the photosensitive layer in the radical polymerization type lithographic printing plate precursor.

  Examples of suitable inorganic fine particles include silica, alumina, magnesium oxide, titanium oxide, magnesium carbonate, calcium alginate, and a mixture thereof. It can be used to enhance the interfacial adhesion due to.

  The average particle size of the inorganic fine particles is preferably 5 nm to 10 μm, more preferably 10 nm to 1 μm. Within this range, both the resin fine particles and the photothermal conversion agent metal fine particles are stably dispersed in the hydrophilic resin, the film strength of the image forming layer is sufficiently maintained, and the hydrophilicity is less likely to cause printing stains. A non-image part can be formed.

  Such inorganic fine particles can be easily obtained as a commercial product such as a colloidal silica dispersion. The content of the inorganic fine particles in the image forming layer is preferably 1.0 to 70% by mass, more preferably 5.0 to 50% by mass, based on the total solid content of the image forming layer.

  In addition to nonionic and anionic surfactants, in addition to nonionic and anionic surfactants, cationic surfactants and fluorine-containing surfactants as described in JP-A-2-195356 are used for the image forming layer. And amphoteric surfactants described in JP-A Nos. 59-121044 and 4-13149 can be added.

  The proportion of the surfactant in the total solid of the image forming layer is preferably 0.05 to 15% by mass, more preferably 0.1 to 5% by mass.

  In addition, in the image forming layer, a dye having a large absorption in the visible light region can be used as an image colorant in order to easily distinguish an image portion from a non-image portion after image formation. Specifically, Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-505 (orientated chemistry) Manufactured by Kogyo Co., Ltd.), Victoria Pure Blue, Crystal Violet (CI 42555), Methyl Violet (CI 42535), Ethyl Violet, Rhodamine B (CI 45170B), Malachite Green (CI 42000), Methylene Blue (CI 522015), etc. And dyes described in No. 293247. Also, pigments such as phthalocyanine pigments, azo pigments, and titanium oxide can be suitably used. The addition amount is suitably 0.01 to 10% by mass with respect to the total solid content of the image forming layer.

  A plasticizer can be added to the image forming layer in order to impart flexibility and the like of the coating film. For example, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate and the like are used.

  The image forming layer is formed by preparing or applying a coating solution by dissolving or dispersing the necessary components described above in water or a mixed solvent to which an organic solvent is added as necessary. The solid content concentration of the coating solution is preferably 1 to 50% by mass.

  Various methods can be used as the coating method. Examples thereof include bar coater coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating, and roll coating. The coating amount (solid content) of the image forming layer on the support obtained after coating and drying varies depending on the use, but is generally preferably 0.5 to 5.0 g / m @ 2, and preferably 0.5 to 2.0 g / m. m2 is more preferred.

  The concentration of the solid content of the image forming layer in the coating solution is preferably 2 to 20% by weight, more preferably 5 to 15% by weight. Within this range, good dispersibility of the fine particles in the coating solution and good fusion of the polymer fine particles when applied to the image forming layer and dried can be obtained.

  In the present invention, a hydrophilic layer can be provided between the support and the image forming layer. A suitable hydrophilic layer is a layer that is three-dimensionally cross-linked and is insoluble in dampening water by lithographic printing using dampening water and / or ink, and preferably contains the following colloids.

  That is, it is a colloid comprising a sol-gel conversion system of oxide or hydroxide of beryllium, magnesium, aluminum, silicon, titanium, boron, germanium, tin, zirconium, iron, vanadium, antimony or transition metal. Further, it may be a colloid composed of a complex of these elements. These colloids have a structure in which the above elements form a network structure through oxygen atoms and at the same time have an unbonded hydroxyl group or alkoxy group, and these are mixed.

  The heat-fusing type lithographic printing original plate of the present invention protects the hydrophilic image-forming layer surface from contamination with lipophilic substances during storage and fingerprint trace contamination due to finger contact during handling. A hydrophilic overcoat layer can be provided.

  As the hydrophilic overcoat layer, the same protective layer as described for the radical polymerization type lithographic printing plate precursor can be used.

  In the heat fusion type lithographic printing plate precursor of the present invention, in order to increase the infrared absorption efficiency and improve the sensitivity, a photothermal conversion agent that absorbs infrared rays and generates heat is used for the image forming layer, the hydrophilic layer, and the overcoat layer. It is preferable to contain in at least one layer.

Next, the polarity conversion type lithographic printing plate precursor will be described.
<Polarity conversion type image forming layer>
The polarity conversion type image forming layer is an image forming layer having a property of changing the hydrophilicity-hydrophobicity of an exposed portion by laser exposure. 1. 1. negative type image forming layer having a property of changing from hydrophilic to hydrophobic by laser exposure; There are two types of positive-type image forming layers having the property of changing from hydrophobic to hydrophilic by laser exposure, and each will be described.

As a negative type image forming layer converted from hydrophilic to hydrophobic by laser exposure, an image forming layer described in JP-A No. 2000-122272 is preferably used. As such an image forming layer, a layer containing a binder polymer having a specific functional group, in particular, at least one group selected from the group consisting of a carboxylic acid group and a carboxylic acid group that undergo decarboxylation by heat is preferable. .
The polymer having at least one group selected from the group consisting of a carboxylic acid group and a carboxylic acid group that undergoes decarboxylation by heat is not particularly limited, but those represented by the following general formula (1) or (2) are preferable. .

In the formula, X represents a group selected from Group 4 to Group 6 elements, the same oxide, the same sulfide, the same selenide and the same telluride, P represents a polymer main chain, and L represents a divalent linkage. R ¹ and R ² each represent a monovalent group that may be the same or different, and M represents a group selected from an alkali metal, an alkaline earth metal, and onium.

R ¹ and R ² are preferably linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, and cyclic alkyl groups having 5 to 10 carbon atoms.
Preferred examples of L include the following structural units or combinations thereof.

X is preferably —CO—, —SO—, or —SO ₂ —.
Preferable examples of M include a monovalent to tetravalent metal cation or an ammonium salt represented by the following general formula (3).

In the formula, R ⁴ , R ⁵ , R ⁶ and R ⁷ each represent a monovalent group which may be the same or different.

The polymer main chain skeleton represented by P is not particularly limited, but preferred examples include (meth) acrylic resins and urethane resins.
The weight average molecular weight of the binder polymer used in the image forming layer is preferably 2000 or more, more preferably 5000 to 300,000, and the number average molecular weight is preferably 800 or more, more preferably 1000. It is in the range of ~ 250,000. The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, and more preferably 1.1 to 10. The binder polymer may be any of a random polymer, a block polymer, a graft polymer, etc., but is preferably a random polymer.
The binder polymer can be used in an amount of 50 to 95% by weight, preferably 70 to 90% by weight, based on the total solid content of the image forming layer. When the addition amount is less than 50% by weight, the printed image becomes unclear, and when the addition amount exceeds 95% by weight, image formation by laser exposure cannot be sufficiently performed.

  In addition to the binder polymer, the image forming layer may contain other components as necessary within a range not impairing the effects of the present invention. As constituent components other than the binder polymer used in the image forming layer, the polymerizable compound, the sensitizing dye, the polymerization initiator, and the heat fusion type lithographic printing plate precursor described for the photosensitive layer in the radical polymerization type lithographic printing plate precursor Examples thereof include various additives such as heat-fusible fine particles, photothermal conversion agents, hydrophilic polymers, inorganic fine particles, surfactants, colorants, and plasticizers described for the photosensitive layer.

  As the positive image forming layer converted from hydrophobic to hydrophilic by laser exposure, an image forming layer described in JP-A No. 11-174585 is preferably used. Such an image forming layer preferably contains a hydrophobic binder polymer (hereinafter also referred to as a heat-sensitive binder polymer) that has a specific functional group and changes to hydrophilicity by energy generated by laser exposure. A heat-sensitive binder polymer is a binder polymer that does not exhibit an affinity such as being normally soluble or swelled in water, and part or all of its structure is changed by heat, and is dissolved or swelled in water. It refers to a binder polymer that exhibits an affinity such as. Examples of such a compound include a hydrophobic binder polymer having a functional group represented by any one of the following general formulas (4) to (8) in the side chain.

In the formula, L represents an organic group composed of a polyvalent nonmetallic atom connected to the hydrophobic binder polymer main chain, R ¹ represents an aryl group, an alkyl group or a cyclic imide group, and R ² and R ³ represent an aryl group. Or an alkyl group, R ⁴ represents an aryl group, an alkyl group or —SO ₂ R ⁵ , R ⁵ represents an aryl group or an alkyl group, and R ⁶ , R ⁷ and R ⁸ each independently represents an aryl group or an alkyl group Represents a group, and any two or three of R ⁶ , R ⁷ and R ⁸ may form a ring. One of R ⁹ and R ¹⁰ represents a hydrogen atom, the other represents a hydrogen atom, an aryl group or an alkyl group, R ¹¹ represents an alkyl group, and R ⁹ and R ¹¹ or R ¹⁰ and R ¹¹ form a ring. May be. L is a polyvalent linking group consisting of non-metallic atoms, and includes 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 100 hydrogen atoms, and 0 It consists of ˜20 sulfur atoms. Specifically, the structural unit described as a preferable example of L in the said General formula (1) or (2), or those combinations can be mentioned.

  The weight average molecular weight of the heat-sensitive binder polymer used in the image forming layer is preferably 2000 or more, more preferably 5000 to 300,000, and the number average molecular weight is preferably 800 or more, more preferably. The range is 1000-250,000. The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, and more preferably 1.1 to 10. The binder polymer may be any of a random polymer, a block polymer, a graft polymer, etc., but is preferably a random polymer.

  The heat-sensitive binder polymer can be used in a proportion of 50 to 90% by weight, preferably 70 to 90% by weight, based on the total solid content of the image forming layer. When the addition amount is less than 50% by weight, the printed image becomes unclear, and when the addition amount exceeds 90% by weight, image formation by laser exposure cannot be sufficiently performed.

  In addition to the binder polymer, the image forming layer may contain other components as necessary within a range not impairing the effects of the present invention. As constituent components other than the binder polymer used in the image forming layer, the polymerizable compound, the sensitizing dye, the polymerization initiator, and the heat fusion type lithographic printing plate precursor described for the photosensitive layer in the radical polymerization type lithographic printing plate precursor Examples thereof include various additives such as heat-fusible fine particles, photothermal conversion agents, hydrophilic polymers, inorganic fine particles, surfactants, colorants, and plasticizers described for the photosensitive layer.

The polarity-converting lithographic printing original plate of the present invention is an overcoat layer on an image forming layer in order to protect the surface of the image forming layer from contamination by a lipophilic substance during storage or fingerprint trace contamination due to finger contact during handling. Can be provided.
As the overcoat layer, the same protective layer as that described for the radical polymerization type lithographic printing plate precursor can be used.

In the lithographic printing plate precursor according to the present invention, the use of a support having a surface with a water-water contact angle of 70 ° or more improves the adhesion between the photosensitive layer and the support interface, resulting in high printing durability. In the non-image area from which the photosensitive layer has been removed, the surface of the support is treated with an aqueous solution having a pH of 2 to 10, whereby the value of the contact angle of water droplets is reduced to 30 ° or less, and the resulting printing plate is being printed It is considered that the stain resistance of the non-image area is improved.

[Preparation method of lithographic printing plate]
A method for preparing the planographic printing plate of the present invention will be described below. The method for producing a lithographic printing plate according to the present invention mainly comprises exposing the lithographic printing plate precursor imagewise, heating the entire plate surface as necessary, and then performing the following plate making steps. (1) Compound having functional group Y (hereinafter also referred to as hydrophilic compound)
(2) pH 2 containing hydrophilizing compound, developed on a printing press using dampening water containing
(3) Development with a developer having a pH of 2 to 10, followed by hydrophilization with an aqueous solution of pH 2 to 10 containing a hydrophilizing compound. By doing this,
The compound having the functional group Y is fixed to the support surface by forming a chemical bond with the compound having the functional group X present on the support surface. As a result, the contact angle of the water droplet on the support surface is 30 ° or less. Can be reduced. The aerial water droplet contact angle on the support surface after the treatment is preferably 25 ° or less, and more preferably 20 ° or less.

[Hydrophilic compound]
In the present invention, in order to reduce the contact angle of the water droplet on the support surface to 30 ° or less, the contact angle of the water droplet on the support surface can be reduced to 30 ° or less by contacting with the compound having the functional group X. A compound having a functional group Y that can be used (hereinafter also referred to as a hydrophilic compound) is used. Such a compound may be any compound as long as it has a property capable of reducing the contact angle of the water droplet on the surface of the support to 30 ° or less by contacting with the compound having the functional group X.

For example, when the compound having the functional group X present on the surface of the support is a compound having the functional group represented by the general formula (0), the compound having the functional group Y includes -COOH,- An acidic functional group selected from SO ₃ H, —PO (OH) (OM) and —B (OH) (OM) (M represents hydrogen, metal cation, ammonium, phosphonium, iodonium, sulfonium, diazonium or azinium). A compound having at least one of is preferably used. Such a hydrophilized compound is adsorbed on the surface of the support when the functional group (Y) interacts with the functional group (X) on the surface of the support, such as acid-base interaction. It is thought to reduce the angle.

The hydrophilic compound used may be either a low molecular compound or a high molecular compound as long as it exhibits the above functions, but is preferably a high molecular compound. By setting it as a high molecular compound, the adsorption | suction power to a support body increases and stain resistance is improved. The polymer compound preferably has a mass average molecular weight of 1000 or more, more preferably 5000 or more.
Specific examples of the hydrophilizing compound used include gum arabic, casein, gelatin, starch derivatives, carboxymethylcellulose and its sodium salt, sodium alginate, vinyl acetate-maleic acid copolymers, styrene-maleic acid copolymer having such acidic functional groups. Polyacrylic acids and their salts, polymethacrylic acids and their salts, copolymers of hydroxyethyl methacrylate, copolymers of hydroxyethyl acrylate, copolymers of hydroxypyrrole methacrylate, copolymers of hydroxypropyl acrylate, copolymers of hydroxybutyl methacrylate, hydroxy Copolymers of butyl acrylate, polyethylene glycols, hydroxypropylene polymers, polyvinyl alcohol Hydrolyzed polyvinyl acetate, polyvinyl formal, polyvinyl butyral, polyvinyl pyrrolidone, acrylamide copolymer, methacrylamide copolymer, N-methylol acrylamide copolymer having a hydrolysis degree of 60 mol% or more, preferably 80 mol% or more, 1- Homopolymers, copolymers and salts thereof of methyl-3-sulfopropylacrylamide, homopolymers, copolymers and salts of methacryloxyethyl phosphate, and the like. In particular, polyacrylic acids having an acidic functional group and salts thereof, polymethacrylic acids and salts thereof are preferably used.

  Further, when the compound having the functional group X present on the surface of the support is a compound having a functional group selected from the functional groups represented by the general formulas (1) to (5), the functional group Y is As the compound having, a compound having a functional group selected from the functional groups represented by the general formulas (6) to (8) is preferably used. A compound having a functional group represented by the general formula (6) or (7) is more preferable, and a compound having a functional group represented by the general formula (7) is particularly preferable. Such a hydrophilized compound is adsorbed on the surface of the support when the functional group (Y) interacts with the functional group (X) on the surface of the support, such as electrostatic interaction, and the water droplet contacts the support. It is thought to reduce the angle.

  The hydrophilic compound used may be either a low molecular compound or a high molecular compound as long as it exhibits the above functions, but is preferably a high molecular compound. By setting it as a high molecular compound, the adsorption | suction power to a support body increases and stain resistance is improved. The polymer compound preferably has a mass average molecular weight of 1000 or more, more preferably 5000 or more, and particularly preferably 10,000 or more.

  Specific examples of hydrophilizing compounds used include gum arabic, casein, gelatin, starch derivatives, carboxymethylcellulose and its sodium salt, cellulose acetate, sodium alginate, vinyl acetate-maleic acid copolymers, styrene-maleic acid copolymers, poly Acrylic acids and their salts, polymethacrylic acids and their salts, polyvinylbenzoic acids and their salts, polyvinylbenzenesulfonic acids and their salts, homopolymers, copolymers and copolymers of 2-acrylamido-2-methylpropanesulfonic acid Examples thereof include salts, homopolymers and copolymers of methacryloyloxyethyl phosphate, and salts thereof.

  As described above, the functional group X is at least one of the functional groups represented by the general formulas (1) to (5), and the functional group Y is represented by the general formulas (6) to (8). In the case of a combination that is at least one of the functional groups, the functional group X is preferably the general formula (1) or (2), and the functional group Y is preferably the general formula (6) or (7). The functional group X is preferably the general formula (1), and the functional group Y is preferably the general formula (7).

  Furthermore, when the compound having the functional group X present on the support surface is a compound having a functional group selected from the functional groups represented by the general formulas (9) to (11), the functional group Y is As the compound having, a compound having a functional group selected from the functional groups represented by the general formulas (12) to (16) is preferably used. A compound having a functional group represented by formula (9) or (10) is more preferred, and a compound having a functional group represented by formula (9) is particularly preferred. Such a hydrophilized compound is adsorbed on the surface of the support when the functional group (Y) interacts with the functional group (X) on the surface of the support, such as electrostatic interaction, and the water droplet contacts the support. It is thought to reduce the angle.

  The hydrophilic compound used may be either a low molecular compound or a high molecular compound as long as it exhibits the above functions, but is preferably a high molecular compound. By setting it as a high molecular compound, the adsorption | suction power to a support body increases and stain resistance is improved. The polymer compound preferably has a mass average molecular weight of 1000 or more, and more preferably 5000 or more.

  Specific examples of the hydrophilizing compound used include starch derivatives such as ammonium-modified starch, homopolymers and copolymers of 3-acrylamidopropyltrimethylammonium chloride, homopolymers and copolymers of 3-acrylamidopropyltrimethylammonium methyl sulfate, 2-methacryloyloxy Examples include homopolymers and copolymers of ethyltrimethylammonium chloride, homopolymers and copolymers of 4-vinylbenzylmethyltriethylammonium chloride, and homopolymers and copolymers of methacryloyloxybutyltriphenylphosphonium chloride.

As described above, the functional group X is at least one of the functional groups represented by the general formulas (9) to (11), and the functional group Y is represented by the general formulas (12) to (16). In the case of a combination that is at least one of the functional groups, the functional group X is preferably the general formula (9) or (10), and the functional group Y is preferably the general formula (12) or (13). The functional group X is preferably the general formula (10), and the functional group Y is preferably the general formula (12).
The combination of the functional group X and the functional group Y is not limited to the above specific example, and the combination of functional groups that can reduce the contact angle of airborne water droplets on the support surface of 70 ° or more to 30 ° or less. Any may be used.

In order to bring the compound having the functional group Y into contact with the compound having the functional group X, any means may be used. From the viewpoint of efficiently bringing both functional groups into contact, it is desirable to carry out in the presence of moisture. Specifically, for example, a method of treating a support having a compound having a functional group X on the surface with an aqueous solution having a pH of 2 to 10 containing a compound having a functional group Y is used. Examples of the form of supplying this aqueous solution include a dampening water at the time of printing, a developing solution, and a processing solution after development. Components other than the compound having the functional group Y can be appropriately adjusted depending on the supply form.

〔exposure〕
The lithographic printing plate precursor according to the invention is preferably image-exposed with a laser having an oscillation wavelength of 350 to 1200 nm.
(1) An infrared laser can be used as the laser light source. The infrared laser used is not particularly limited, but a solid laser or a semiconductor laser that emits infrared light having a wavelength of 760 to 1200 nm is preferable. The output of the infrared laser is 100m
It is preferable that it is W or more. In order to shorten the exposure time, it is preferable to use a multi-beam laser device. The exposure time per pixel is preferably within 20 μsec. Moreover, it is preferable that irradiation energy amount is 10-300 mJ / cm < ² >.

(2) As a laser light source, a 405 nm or 830 nm semiconductor laser, an FD-YAG laser, or the like is used. In recent years, from the viewpoint of system cost and handleability,
A CTP system equipped with a 405 nm semiconductor laser is widely used. For example, 350
Inner drum exposure apparatus equipped with a light source having an oscillation wavelength in the range of nm to 450 nm [the light beam spot shape of the light beam emitted from the light source divides the light beam into an ordinary ray and an extraordinary ray in parallel with an equal amount of light, It is possible to record an image by exposing the light beam spot shape after placing the above-described lithographic printing plate precursor on the sub-scanning direction so that the two beam spots partially overlap each other. It is.
The exposure apparatus used in the present invention may be any of an internal drum system, an external drum system, a flat bed system, and the like. Further, by simultaneously recording an image by the multi-beam exposure method, a highly accurate image can be recorded at a high speed.
Further, at the time of exposure of the lithographic printing plate precursor according to the present invention, image recording can be performed on an FM screen.

〔heating〕
In the present invention, the entire surface of the lithographic printing plate precursor exposed imagewise may be heated between exposure and development, if necessary. By such heating, an image forming reaction in the photosensitive layer is promoted, and advantages such as improvement in sensitivity and printing durability and stabilization of sensitivity may occur.
Moreover, when it has a protective layer on a photosensitive layer, it is also preferable to perform a water washing process before image development processing.

[Plate making]
The lithographic printing plate precursor according to the present invention is imagewise exposed with a semiconductor laser or a solid laser as described above, and if necessary after heating the entire surface as described above, the oil-based ink and the above hydrophilic ink without any development processing steps. An aqueous component containing a chemical compound can be supplied for printing. Specifically, after exposing the lithographic printing plate precursor with a laser and heating the entire plate surface in an oven,
A method of printing by mounting on a printing machine without going through a development processing step. After mounting a lithographic printing plate precursor on a printing machine, exposing it with a laser on the printing machine and heating the entire plate surface on the printing machine, then developing. Examples include a method of printing without passing through a processing step.

For example, in one aspect of the negative on-press development type lithographic printing plate precursor, the lithographic printing plate precursor is exposed imagewise with a laser and then contains a hydrophilic compound without undergoing a development processing step such as a wet development processing step. When supplying water-based components and oil-based inks to be printed,
The photosensitive layer cured by exposure forms an oil-based ink receiving portion having an oleophilic surface. on the other hand,
In the unexposed area, the uncured photosensitive layer is dissolved or dispersed and removed by the aqueous component and / or oil-based ink containing the supplied hydrophilic compound, and the surface of the support is exposed in that area. As a result, the aqueous component adheres to the exposed support surface, and the oil-based ink is deposited on the photosensitive layer in the exposed area, and printing is started. Here, an aqueous component containing a hydrophilizing compound or an oil-based ink may be supplied to the printing plate first, but the aqueous component containing the hydrophilizing compound is contaminated by the photosensitive layer in the unexposed area. It is preferable to supply the oil-based ink first from the viewpoint of preventing the ink. As the aqueous component and the oil-based ink containing the hydrophilic compound, those obtained by adding a hydrophilic compound to dampening water for ordinary lithographic printing and printing inks are used.
In this way, the lithographic printing plate precursor is subjected to on-press development on a printing machine and used as it is for printing a large number of sheets.

Further, in another aspect of the plate making method of the lithographic printing plate of the present invention, after the image-wise exposure with a laser as described above and the entire plate surface is heated as necessary, the automatic processor equipped with a rubbing member is used to A lithographic printing plate can also be obtained by removing the photosensitive layer in the non-exposed area by rubbing the plate surface with a rubbing member in the presence of a developer containing a hydrophilizing compound and having a pH of 2 to 10.
Further, in another aspect of the plate making method of the lithographic printing plate of the present invention, the pH is measured by an automatic processor equipped with a rubbing member after imagewise exposure with a laser and heating the entire plate surface as necessary, as described above. After removing the photosensitive layer in the non-exposed area by rubbing the plate surface with a rubbing member in the presence of a developer of 2 to 10, an aqueous solution containing the hydrophilic compound (hereinafter referred to as a hydrophilized aqueous solution) on the exposed support surface. Lithographic printing plates can also be obtained by bringing them into contact with each other by a method such as immersion, spraying or coating.
The developer used in the present invention is preferably, for example, water alone or an aqueous solution containing water as a main component (containing 60% by mass or more of water). An aqueous solution containing a surfactant (anionic, nonionic, cationic, etc.) or an aqueous solution containing a water-soluble polymer compound is preferred. In particular, an aqueous solution containing both a surfactant and a water-soluble polymer compound is preferable. The pH of the developer is more preferably 3-8, still more preferably 4-7.

Examples of the anionic surfactant used in the present invention include fatty acid salts, abietic acid salts,
Hydroxyalkanesulfonates, alkanesulfonates, dialkylsulfosuccinates, linear alkylbenzenesulfonates, branched alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkylphenoxypolyoxyethylenepropylsulfonates, polyoxyethylenealkyl Sulfophenyl ether salts, N-methyl-N-oleyl taurine sodium, N-alkylsulfosuccinic acid monoamide disodium salt, petroleum sulfonates, sulfated castor oil, sulfated beef tallow oil, sulfate esters of fatty acid alkyl esters, alkyl Sulfate esters, polyoxyethylene alkyl ether sulfates, fatty acid monoglyceride sulfates, polyoxyethylene alkyl phenyl ether sulfates Tell salt, polyoxyethylene styryl phenyl ether sulfate ester salt, alkyl phosphate ester salt, polyoxyethylene alkyl ether phosphate ester salt, polyoxyethylene alkyl phenyl ether phosphate ester salt, partially saponified styrene-maleic anhydride copolymer , Partially saponified products of olefin-maleic anhydride copolymer, naphthalene sulfonate formalin condensate, and the like. Among these, dialkyl sulfosuccinates, alkyl sulfate esters and alkyl naphthalene sulfonates are particularly preferably used.

It does not specifically limit as a cationic surfactant used for this invention, A conventionally well-known thing can be used. Examples thereof include alkylamine salts, quaternary ammonium salts, polyoxyethylene alkylamine salts, and polyethylene polyamine derivatives.
Nonionic surfactants used in the present invention include polyethylene glycol type higher alcohol ethylene oxide adducts, alkylphenol ethylene oxide adducts,
Fatty acid ethylene oxide adduct, polyhydric alcohol fatty acid ester ethylene oxide adduct, higher alkylamine ethylene oxide adduct, fatty acid amide ethylene oxide adduct, fat and oil ethylene oxide adduct, polypropylene glycol ethylene oxide adduct, dimethylsiloxane-ethylene oxide Block copolymer, dimethylsiloxane- (propylene oxide-ethylene oxide) block copolymer, fatty acid ester of polyhydric alcohol type, fatty acid ester of pentaerythritol, fatty acid ester of sorbitol and sorbitan, fatty acid ester of sucrose, polyhydric alcohol Alkyl ethers, fatty acid amides of alkanolamines, and the like.

In the present invention, ethylene oxide adduct of sorbitol and / or sorbitan fatty acid ester, polypropylene glycol ethylene oxide adduct, dimethylsiloxane-ethylene oxide block copolymer, dimethylsiloxane- (propylene oxide-ethylene oxide) block copolymer, polyhydric alcohol Fatty acid esters are more preferred.
Further, from the viewpoint of stable solubility or turbidity in water, the nonionic surfactant used in the developer of the present invention is HLB (Hydrophile-Lipophile).
The (Balance) value is preferably 6 or more, and more preferably 8 or more.
Also, acetylene glycol-based and acetylene alcohol-based oxyethylene adducts, fluorine-based and silicon-based surfactants can be used in the same manner.
As the surfactant used in the developer of the present invention, a nonionic surfactant is particularly suitable from the viewpoint of foam suppression.
The surfactants may be used alone or in combination of two or more. The content of the surfactant in the developer is preferably from 0.01 to 10% by mass, more preferably from 0.01 to 5% by mass.
It is.

Examples of the water-soluble polymer compound used in the developer of the present invention include soybean polysaccharide, modified starch, gum arabic, dextrin, and a cellulose derivative (for example, carboxymethyl cellulose,
Carboxyethyl cellulose, methyl cellulose, etc.) and modified products thereof, pullulan, polyvinyl alcohol and derivatives thereof, polyvinyl pyrrolidone, polyacrylamide and acrylamide copolymer, vinyl methyl ether / maleic anhydride copolymer, vinyl acetate / maleic anhydride copolymer And styrene / maleic anhydride copolymer.
A well-known thing can be used for the said soybean polysaccharide, for example, there exists a brand name Soya Five (made by Fuji Oil Co., Ltd.) as a commercial item, and the thing of various grades can be used. What can be preferably used is one in which the viscosity of a 10 mass% aqueous solution is in the range of 10 to 100 mPa / sec.
As the modified starch, known ones can be used, and starch such as corn, potato, tapioca, rice, wheat is decomposed with acid or enzyme in the range of 5 to 30 glucose residues per molecule,
Furthermore, it can be made by a method of adding oxypropylene in an alkali.

Two or more water-soluble polymer compounds can be used in combination. The content of the water-soluble polymer compound in the developer is preferably from 0.1 to 20% by mass, more preferably from 0.5 to 10% by mass.
Further, the developer of the present invention may contain an organic solvent. As an organic solvent that can be contained,
For example, aliphatic hydrocarbons (hexane, heptane, Isopar E, H, G (Essochemistry (
Co., Ltd.), gasoline, kerosene, etc.), aromatic hydrocarbons (toluene, xylene, etc.), halogenated hydrocarbons (methylene dichloride, ethylene dichloride, tricrene, monochlorobenzene, etc.) and polar solvents.

Polar solvents include alcohols (methanol, ethanol, propanol, isopropanol, benzyl alcohol, ethylene glycol monomethyl ether, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether , Propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, etc.) , (Acetone, methyl ethyl ketone, ethyl butyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), esters (ethyl acetate, propyl acetate, butyl acetate, amyl acetate, benzyl acetate, methyl lactate, butyl lactate, ethylene glycol monobutyl acetate, propylene Glycol monomethyl ether acetate, diethylene glycol acetate, diethyl phthalate, butyl levulinate, etc.) and others (triethyl phosphate, tricresyl phosphate, N-phenylethanolamine, N-phenyldiethanolamine, etc.).
When the organic solvent is insoluble in water, it can be used after being solubilized in water using a surfactant or the like. When the developer contains an organic solvent, from the viewpoint of safety and flammability,
The concentration of the solvent is preferably less than 40% by mass.

In addition to the above, the developer of the present invention includes preservatives, chelate compounds, antifoaming agents, organic acids, inorganic acids,
Inorganic salts and the like can be contained.
Preservatives include phenol or derivatives thereof, formalin, imidazole derivatives, sodium dehydroacetate, 4-isothiazolin-3-one derivatives, benzoisothiazoline-
3-ones, benztriazole derivatives, amiding anidine derivatives, quaternary ammonium salts, pyridine, quinoline, guanidine and other derivatives, diazines, triazole derivatives, oxazole, oxazine derivatives, 2-bromo-2-nitropropane-based nitrobromoalcohols 1,3-diol, 1-dibromo-1-nitro-2-ethanol, 1,1-dibromo-1-nitro-2-propanol and the like can be preferably used.
Examples of the chelate compound include ethylenediaminetetraacetic acid, potassium salt thereof, sodium salt thereof; diethylenetriaminepentaacetic acid, potassium salt thereof, sodium salt thereof; triethylenetetraminehexaacetic acid, potassium salt thereof, sodium salt thereof, hydroxyethylethylenediaminetriacetic acid Nitrilotriacetic acid, sodium salt; 1-hydroxyethane-1,1-diphosphonic acid, potassium salt, sodium salt; aminotri (methylenephosphonic acid), potassium salt, sodium salt And organic phosphonic acids and phosphonoalkanetricarboxylic acids. Organic amine salts are also effective in place of the sodium and potassium salts of the chelating agents.

As the antifoaming agent, a general silicon-based self-emulsifying type, emulsifying type, or nonionic surfactant having a HLB of 5 or less can be used. Silicon antifoaming agents are preferred.
Among them, emulsification dispersion type and solubilization can be used.
Examples of organic acids include citric acid, acetic acid, succinic acid, malonic acid, salicylic acid, caprylic acid, tartaric acid, malic acid, lactic acid, levulinic acid, p-toluenesulfonic acid, xylenesulfonic acid, phytic acid, and organic phosphonic acid. . The organic acid can also be used in the form of its alkali metal salt or ammonium salt.
Examples of inorganic acids and inorganic salts include phosphoric acid, metaphosphoric acid, primary ammonium phosphate, secondary ammonium phosphate, primary sodium phosphate, secondary sodium phosphate, primary potassium phosphate, secondary potassium phosphate, Examples include sodium tripolyphosphate, potassium pyrophosphate, sodium hexametaphosphate, magnesium nitrate, sodium nitrate, potassium nitrate, ammonium nitrate, sodium sulfate, potassium sulfate, ammonium sulfate, sodium sulfite, ammonium sulfite, sodium hydrogen sulfate, nickel sulfate and the like.

The developer can be used as a developer and a developer replenisher for the exposed lithographic printing plate precursor, and is preferably applied to an automatic processor described later. When developing using an automatic processor, the developing solution becomes fatigued according to the amount of processing, so the processing capability may be restored using a replenisher or a fresh developer. This replenishing method is also preferably applied to the plate making method of the lithographic printing plate precursor according to the present invention.
The development treatment with an aqueous solution having a pH of 2 to 10 in the present invention can be preferably carried out by an automatic processor equipped with a developer supply means and a rubbing member. As an automatic processor, for example, a rubbing process is performed while transporting a lithographic printing plate precursor after image exposure.
No. 1, U.S. Pat. No. 5,148,746, which performs rubbing treatment on an automatic processing machine described in JP-A-60-59351 and a planographic printing plate precursor after image exposure set on a cylinder while rotating the cylinder No. 5,568,768 and an automatic processor described in British Patent No. 2297719. Among these, an automatic processor using a rotating brush roll as the rubbing member is particularly preferable.

The rotating brush roll that can be preferably used in the present invention can be appropriately selected in consideration of the difficulty of scratching the image area and the stiffness of the support of the lithographic printing plate precursor. As the rotating brush roll, a known one formed by planting a brush material on a plastic or metal roll can be used. For example, Japanese Patent Laid-Open No. 58-159533 and Japanese Patent Laid-Open No. 3-100
No. 554 and those described in Japanese Utility Model Publication No. 62-167253,
A brush roll can be used in which metal or plastic groove molds in which brush materials are implanted in rows are wound radially around a plastic or metal roll as a core without gaps.
Examples of brush materials include plastic fibers (for example, polyesters such as polyethylene terephthalate and polybutylene terephthalate, polyamides such as nylon 6.6 and nylon 6.10, polyacrylics such as polyacrylonitrile and poly (meth) acrylate). And polyolefin synthetic fibers such as polypropylene and polystyrene). For example, the fiber hair diameter is 20 to 400 μm, and the hair length is 5 to 30 mm.
Can be preferably used. The outer diameter of the rotating brush roll is preferably 30 to 200 mm,
The peripheral speed at the tip of the brush rubbing the printing plate is preferably 0.1 to 5 m / sec. It is preferable to use two or more rotating brush rolls.

The rotating direction of the rotating brush roll used in the present invention may be the same or opposite to the conveying direction of the planographic printing plate precursor of the present invention. As described above, when two or more rotating brush rolls are used, it is preferable that at least one rotating brush roll rotates in the same direction and at least one rotating brush roll rotates in the opposite direction. This further ensures the removal of the photosensitive layer in the non-image area. Furthermore, it is also effective to swing the rotating brush roll in the direction of the rotation axis of the brush roll.
Although the said developing solution can be used at arbitrary temperature, Preferably it is 10 to 50 degreeC.

The hydrophilic aqueous solution used in the present invention is preferably, for example, a hydrophilic compound-containing aqueous solution containing water as a main component (containing 60% by mass or more of water). The content of the hydrophilic compound is preferably 1% by mass to 40% by mass, more preferably 2% by mass to 30% by mass, and particularly preferably 3% by mass to 20% by mass in the hydrophilized aqueous solution. As components other than the hydrophilic compound,
In addition to the pH adjuster, the aforementioned surfactant, organic solvent, preservative, chelate compound, antifoaming agent, organic acid, inorganic acid, inorganic salt and the like can be contained. These components can be used by appropriately adjusting the content. The pH of the hydrophilized aqueous solution is preferably 2 to 10, more preferably 3 to 3.
8, more preferably 4-7.
In the present invention, the lithographic printing plate treated as described above can be optionally washed with water, dried and desensitized. In the desensitizing treatment, a known desensitizing solution can be used.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these.
[Examples 1 to 66 and Comparative Examples 1 to 46]

(Preparation of aluminum support 1)
In order to remove rolling oil on the surface of an aluminum plate (material: JIS A1050) having a thickness of 0.3 mm, a degreasing treatment was performed at 50 ° C. for 30 seconds using a 10 mass% sodium aluminate aqueous solution, and then the bristle diameter was set to 0.00. The aluminum surface was grained using ^three 3 mm bundled nylon brushes and a pumice-water suspension (specific gravity 1.1 g / cm ³ ) having a median diameter of 25 μm and washed well with water. This plate was etched by being immersed in a 25 mass% sodium hydroxide aqueous solution at 45 ° C for 9 seconds, washed with water, further immersed in a 20 mass% nitric acid aqueous solution at 60 ° C for 20 seconds, and washed with water. At this time, the etching amount of the grained surface was about 3 g / m ² .
Next, an electrochemical roughening treatment was performed continuously using an alternating voltage of 60 Hz. The electrolytic solution at this time is a 1% by mass aqueous solution of nitric acid (containing 0.5% by mass of aluminum ions), a liquid temperature of 5
It was 0 ° C. In the AC power supply waveform, the time TP until the current value reaches the peak from zero is 0.
An electrochemical roughening treatment was performed using a trapezoidal rectangular wave alternating current of 8 msec, a duty ratio of 1: 1, and a carbon electrode as a counter electrode. Ferrite was used for the auxiliary anode. The current density was 30 A / dm ² at the peak current value, and 5% of the current flowing from the power source was shunted to the auxiliary anode.
The amount of electricity in nitric acid electrolysis was 175 C / dm ² when the aluminum plate was the anode.
Then, water washing by spraying was performed.

Next, a 0.5 mass% hydrochloric acid aqueous solution (containing 0.5 mass% aluminum ions), a liquid temperature of 50
An electrolytic surface roughening treatment was performed in the same manner as in nitric acid electrolysis under the condition of an electric quantity of 50 C / dm ² when the aluminum plate was an anode with an electrolytic solution at ° C, and then washed with water by spraying. .
The plate was provided with a DC anodized film of 2.5 g / m ² at a current density of 15 A / dm ² using a 15% by mass sulfuric acid aqueous solution (containing 0.5% by mass of aluminum ions) as an electrolyte, then washed with water and dried. An aluminum support 1 was prepared.
The center line average roughness (Ra) of the support thus obtained was measured using a needle having a diameter of 2 μm and found to be 0.51 μm.

<Preparation of lithographic printing plate precursor supports 1-8>
On the aluminum support 1 obtained as described above, a surface treatment solution 1 having the following composition was applied and dried at 100 ° C. for 3 minutes. The coating amount of the obtained surface treatment layer was 10 mg /
It was m ^2.

(Surface treatment liquid 1)
・ Surface treatment compounds listed in Table 1 0.50 g
・ N-methylpyrrolidone 49.00g
・ Methanol 450.00g
・ Water 1.50g
・ Phosphoric acid 0.01g

<Preparation of lithographic printing plate precursors 9 to 16>
On the aluminum support 1 obtained as described above, a surface treatment liquid 2 having the following composition was applied and dried at 100 ° C. for 3 minutes. The coating amount of the obtained surface treatment layer was 7 mg / m
² .

(Surface treatment liquid 2)
・ Surface treatment compounds listed in Table 1 0.50 g
・ N-methylpyrrolidone 49.00g
・ Methanol 450.00g
・ Water 1.50g

  The aerial water droplet contact angles of the lithographic printing plate precursor supports 1 to 16 thus obtained were measured according to the measurement method described above. The results are shown in Table 1.

  The lithographic printing plate precursor supports 1 to 16 were cut to a size of 3 × 3 cm and immersed in 20 mL of the following aqueous solutions 1 to 7 (both pH 4.5 to 5.5) at a temperature of 25 ° C. for 1 minute. . Thereafter, it was washed with distilled water, dried at 100 ° C. for 1 minute, and a lithographic printing plate precursor support treated with a hydrophilic compound was obtained.

(Aqueous solutions 1-7)
・ Water 100.00g
・ Benzyl alcohol 1.00g
・ Polyoxyethylene naphthyl ether 1.00g
(Average number of oxyethylene n = 13)
・ Dioctylsulfosuccinate sodium salt 0.50 g
-1.00 g of hydrophilized compounds listed in Table 1
・ Ethylene glycol 0.50g
・ Primary ammonium phosphate 0.05g
・ Citric acid 0.05g
・ Ethylenediaminetetraacetate tetrasodium salt 0.05g

The aerial water droplet contact angle of the lithographic printing plate precursor support after the treatment was measured in the same manner as described above. The results are shown in Table 1.

As is apparent from the results in Table 1, the support for a lithographic printing plate precursor according to the present invention (on its surface,
When a compound having a functional group X is treated with an aqueous solution containing a hydrophilic compound (a compound having a functional group Y), the aerial water droplet contact angle on the surface is reduced from 70 ° to 30 °. On the other hand, when treated with an aqueous solution containing no hydrophilizing compound, no decrease in the contact angle of the water droplets is observed. Moreover, in the support body which does not have the compound which has the functional group X on the surface, although an air drop contact angle is 70 degrees or more, the treatment with the aqueous solution containing a hydrophilization compound makes the air drop contact angle small. At most, it is reduced to 60 °.

<Preparation of lithographic printing plate precursors 1 to 16>
On the above lithographic printing plate precursor support, a photosensitive layer coating solution 1 having the following composition was applied,
Dry at 80 ° C. for 1 minute. The coating amount of the obtained photosensitive layer was 1.2 g / m ² .

(Photosensitive layer coating solution 1)
-0.54g of the following binder polymer (1)
・ Polymerizable compound (1) 0.48 g
Isocyanuric acid EO-modified triacrylate (Aronix M-315, manufactured by Toa Gosei Co., Ltd.)
・ The following sensitizing dye (1) 0.06 g
・ The following polymerization initiator (1) 0.10 g
・ The following co-sensitizer (1) 0.07 g
・ 0.40 g of ε-phthalocyanine pigment dispersion
[Pigment: 15 parts by mass, allyl methacrylate / methacrylic acid (80/20) copolymer as dispersant: 10 parts by mass, cyclohexanone /
Methoxypropyl acetate / 1-methoxy-2-propanol = 15
Part by mass / 20 parts by mass / 40 parts by mass]
・ Methyl ethyl ketone 4.80g
・ Dimethyl sulfoxide 4.80g

A protective layer coating solution 1 having the following composition was applied on the photosensitive layer using a bar so that the dry coating amount was 0.75 g / m ^2, and then dried at 125 ° C. for 70 seconds to form a protective layer. Then, lithographic printing plate precursors 1 to 16 were prepared.

(Protective layer coating solution 1)
Polyvinyl alcohol (degree of saponification: 98 mol%, degree of polymerization: 500) 40 g
・ Polyvinylpyrrolidone (molecular weight: 50,000) 5g
・ Poly [vinyl pyrrolidone / vinyl acetate (1/1)] (molecular weight: 70,000) 0.5 g
・ Surfactant (Emalex 710, manufactured by Nippon Emulsion Co., Ltd.) 0.5g
・ 950g of water

(1) Exposure, development and printing Each of the above lithographic printing plate precursors 1 to 16 was subjected to imagewise exposure using a 405 nm semiconductor laser having an output of 100 mW while changing the energy density.
Thereafter, using the aqueous solutions 1 to 7, development processing was performed with an automatic development processor having a structure shown in FIG. 1 to prepare a lithographic printing plate (no heating). The automatic developing processor has two rotating brush rolls, and the first rotating brush roll is made of polybutylene terephthalate fiber (hair diameter 2).
A brush roll having an outer diameter of 90 mm in which 00 μm and a hair length of 17 mm are implanted, is rotated 200 times per minute in the same direction as the conveying direction (peripheral speed of the brush tip is 0.94 m / sec), and the second rotating brush roll Is a brush roll with an outer diameter of 60 mm in which fibers made of polybutylene terephthalate (hair diameter: 200 μm, hair length: 17 mm) are implanted at a rate of 2 per minute in the direction opposite to the conveying direction.
00 rotation (peripheral speed of the brush tip 0.63 m / sec). Transportation of lithographic printing plate precursor is
It implemented at the conveyance speed of 100 cm / min.

The aqueous solution was showered from the spray pipe by a circulation pump and supplied to the plate surface. The tank capacity of the aqueous solution was 10 liters.
On the other hand, the lithographic printing plate precursor was placed in an oven within 30 seconds after the laser image-like exposure, and the entire surface of the lithographic printing plate precursor was heated by blowing hot air, and held at 110 ° C. for 15 seconds. Then 30
Within seconds, the same development treatment as described above was performed to prepare a lithographic printing plate (with heating).
Next, the lithographic printing plate (without heating) and the lithographic printing plate (with heating) are attached to a printing machine SOR-M manufactured by Heidelberg, and dampening water (EU-3 (Effect manufactured by FUJIFILM Corporation) / water /
Using isopropyl alcohol = 1/89/10 (volume ratio)) and TRANS-G (N) black ink (manufactured by Dainippon Ink & Chemicals, Inc.), printing was performed at a printing speed of 6000 sheets per hour.

(2) Evaluation The printing durability and stain resistance were evaluated as follows. The results are shown in Table 2.
<Print durability>
When the above-mentioned printing was performed and the number of printed sheets increased, the photosensitive layer was gradually worn out and the ink receptivity was lowered, so that the ink density in the printed material was lowered. In a printing plate exposed at the same exposure amount (energy density), the printing durability was relatively evaluated by the number of printed sheets when the ink density (reflection density) was reduced by 0.1 from the start of printing. That is, the calculation was performed according to the following formula with Comparative Example 7 as a reference (100). Large numbers indicate high printing durability.
Printing durability = (Number of printing durability of target lithographic printing plate) / (Number of printing durability of standard lithographic printing plate) × 100

<Stain resistance>
After the start of printing, the 500th printed material was taken out and the stain resistance was evaluated relative to the density of the ink adhering to the non-image area. That is, the calculation was performed according to the following formula with Comparative Example 7 as a reference (100). A large number indicates that the ink density adhered to the non-image area is low, that is, the stain resistance is good.
Stain resistance = (Non-image area ink density of standard lithographic printing plate) / (Non-image area ink density of target lithographic printing plate) × 100

As is clear from the results in Table 2, the lithographic printing plate precursor according to the present invention can provide a lithographic printing plate having both high printing durability and excellent stain resistance by simple treatment.

[Examples 67 to 77 and Comparative Examples 47 to 51]
<Preparation of planographic printing plate precursors 17 to 32>
The lithographic printing plate precursors 1 to 16 except that the photosensitive layer coating solution 1 is changed to the following photosensitive layer coating solution 2
The lithographic printing plate precursors 17 to 32 were prepared in the same manner as described above.

(Photosensitive layer coating solution 2)
・ The following binder polymer (2) 0.54 g
-0.48 g of the following polymerizable compound (2)
-0.06 g of the above sensitizing dye (1)
・ The above polymerization initiator (1) 0.18 g
・ Cosensitizer (1) 0.07g
・ 0.40 g of ε-phthalocyanine pigment dispersion
[Pigment: 15 parts by mass, allyl methacrylate / methacrylic acid (80/20) copolymer as dispersant: 10 parts by mass, cyclohexanone /
Methoxypropyl acetate / 1-methoxy-2-propanol = 15
Part by mass / 20 parts by mass / 40 parts by mass]
・ Thermal polymerization inhibitor 0.01g
N-nitrosophenylhydroxylamine aluminum salt, the following fluorosurfactant (1) 0.001 g
・ Polyoxyethylene-polyoxypropylene condensate 0.04g
(Asahi Denka Kogyo Co., Ltd., Pluronic L44)
・ Tetraethylamine hydrochloride 0.01g
・ 3.5 g of 1-methoxy-2-propanol
・ Methyl ethyl ketone 8.0g

The obtained lithographic printing plate precursors 17 to 32 were exposed, developed and printed in the same manner as in Example 1 except that the aqueous solution 5 was used, and evaluated in the same manner. Comparative Example 47 was used as the evaluation standard. The results are shown in Table 3.

As is apparent from the results in Table 3, the lithographic printing plate precursor according to the present invention can provide a lithographic printing plate having both high printing durability and excellent stain resistance by simple treatment.

[Examples 78 to 88 and Comparative Examples 52 to 56]
(Preparation of aluminum support 2)
An aluminum plate (material: JIS A1050) having a thickness of 0.3 mm is subjected to the following steps (
a) to (k) were carried out in this order for surface treatment.

(A) Mechanical surface-roughening treatment A roller-type nylon brush rotates while supplying a suspension (specific gravity 1.12) of an abrasive (silica sand) and water as a polishing slurry to the surface of an aluminum plate. 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. 3 rotating brushes
Used this book. 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) Alkaline etching treatment The obtained aluminum plate is sprayed with a caustic soda aqueous solution (concentration 26 mass%, aluminum ion concentration 6.5 mass%) at a temperature of 70 ° C. to dissolve the aluminum plate 6 g / m ^2. did. Thereafter, washing with water was performed using well water.

(C) Desmutting treatment The desmutting treatment was performed by spraying with a 1% by mass aqueous solution of nitric acid at a temperature of 30 ° C. (containing 0.5% by mass of aluminum ions), and then washed with water by spraying. As the nitric acid aqueous solution used for desmutting, the waste solution of the electrolytic solution in the following step (d) was used.

(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. AC power supply waveform has zero time TP until the current value reaches the peak from zero
. An electrochemical roughening treatment was performed using a trapezoidal rectangular wave for 8 ms, a DUTY ratio of 1: 1, with 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 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) Alkaline etching treatment An aluminum plate is made of caustic soda concentration of 26% by mass and aluminum ion concentration of 6.5% by mass.
Etching treatment by spraying with aqueous solution is performed at 32 ° C., and aluminum plate is 0.20 g /
m ^{2 was} dissolved to remove the smut component mainly composed of aluminum hydroxide formed in the step (d), and the edge portion of the generated pit was dissolved to smooth the edge portion. Thereafter, washing with water was performed using well water. The etching amount was 3.5 g / m ² .

(F) Desmutting treatment A 15% by mass aqueous solution of nitric acid having a temperature of 30 ° C. (including 4.5% by mass of aluminum ions)
Then, the desmut treatment was performed by spraying, and then washed with water using well water.
As the nitric acid aqueous solution used for desmutting, the waste solution of the electrolytic solution in step (d) was used.

(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 is a 7.5 g / liter aqueous solution of hydrochloric acid (containing 5 g / liter of aluminum ions).
The temperature was 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 made with caustic soda concentration of 26% by mass and aluminum ion concentration of 6.5% by mass.
Etching by spraying with an aqueous solution at 32 ° C., and an aluminum plate of 0.10 g /
m ^{2 was} dissolved to remove the smut component mainly composed of aluminum hydroxide formed in the step (g), and the edge portion of the generated pit was dissolved to smooth the edge portion. Thereafter, washing with water was performed using well water.

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

(J) Anodizing treatment As an electrolytic solution, sulfuric acid concentration of 170 g / liter aqueous solution (0.5% by mass of aluminum ions)
Including. ) And an anodizing treatment at a temperature of 43 ° C. was performed. The current density was about 30A / dm ^2. Thereafter, washing with water was performed using well water. The final oxide film amount is 2.7
g / m ² .

(K) Alkali metal silicate treatment The alkali metal silicate treatment (silicate treatment) was performed by immersing the aluminum plate in a 1 mass% aqueous solution of sodium silicate No. 3 having a temperature of 30 ° C. for 10 seconds. Then, the aluminum support body was produced by performing the water washing by the spray using well water. The amount of silicate adhered was 3.6 mg / m ² .

<Preparation of lithographic printing plate precursor supports 17-24>
On the aluminum support 2 obtained as described above, a surface treatment liquid 3 having the following composition was applied and dried at 100 ° C. for 3 minutes. The coating amount of the obtained surface treatment layer was 10 mg /
It was m ^2.

(Surface treatment liquid 3)
・ Surface treatment compounds listed in Table 4 0.50 g
・ N-methylpyrrolidone 49.00g
・ Methanol 450.00g
・ Water 1.50g
・ Phosphoric acid 0.01g

<Preparation of lithographic printing plate supports 25-32>
On the aluminum support 2 obtained as described above, a surface treatment liquid 4 having the following composition was applied and dried at 100 ° C. for 3 minutes. The coating amount of the obtained surface treatment layer was 7 mg / m ² .

(Surface treatment liquid 4)
・ Surface treatment compounds listed in Table 4 0.50 g
・ N-methylpyrrolidone 49.00g
・ Methanol 450.00g
・ Water 1.50g

The aerial water droplet contact angles of the lithographic printing plate supports 17 to 32 thus obtained were measured according to the measurement method described above. The results are shown in Table 4.

The above lithographic printing plate precursor supports 17 to 32 were cut into a size of 3 × 3 cm and immersed in 20 mL of the aqueous solution 1 at a temperature of 25 ° C. for 1 minute. Thereafter, the support was washed with distilled water, dried at 100 ° C. for 1 minute, and a lithographic printing plate precursor support treated with a hydrophilic compound was obtained.

The aerial water droplet contact angle of the lithographic printing plate precursor support after the treatment was measured in the same manner as described above. The results are shown in Table 4.

<Preparation of lithographic printing plate precursors 33-48>
A photosensitive layer coating solution 3 having the following composition is bar-coated on each of the above lithographic printing plate precursor supports, and 70
Oven drying was performed at 60 ° C. for 60 seconds to form a photosensitive layer having a dry coating amount of 1.0 g / m ² .

The photosensitive layer coating solution 3 was prepared by mixing the following photosensitive solution (1) and microcapsule solution (1) immediately before coating.
Photosensitive solution (1)
・ The following binder polymer (3) 0.162 g
・ The following polymerization initiator (2) 0.160 g
・ The following polymerization initiator (3) 0.180 g
・ The following infrared absorber (1) 0.020 g
・ Polymerizable compound 0.385 g
Aronix M-215 (manufactured by Toa Gosei Co., Ltd.)
・ 0.044 g of the above fluorosurfactant (1)
・ Methyl ethyl ketone 1.091g
・ 1-methoxy-2-propanol 8.210 g

Microcapsule liquid (1)
・ Microcapsule (1) prepared as follows: 2.640 g
・ Water 2.425g

Preparation of microcapsule (1) As an oil phase component, trimethylolpropane and xylene diisocyanate adduct (manufactured by Mitsui Takeda Chemical Co., Ltd., Takenate D-110N, 75 mass% ethyl acetate solution), 10 g, Aronix SR-399 ( Toagosei Co., Ltd. (6.00 g) and Pionein A-41C (Takemoto Yushi Co., Ltd.) 0.12 g were dissolved in ethyl acetate 16.67 g. PVA-2 as water phase component
37.5 g of a 4 mass% aqueous solution of 05 was prepared. The oil phase component and the aqueous phase component were mixed and emulsified for 10 minutes at 12000 rpm using a homogenizer. The obtained emulsion was added to distilled water 25.
After stirring at room temperature for 30 minutes, the mixture was stirred at 40 ° C. for 2 hours. The microcapsule solution thus obtained was diluted with distilled water so that the solid content concentration was 15% by mass. The average particle size of the microcapsules was 0.2 μm.

The following protective layer coating solution 2 was bar coated on the photosensitive layer and oven dried at 125 ° C. for 75 seconds to form a protective layer having a dry coating amount of 0.15 g / m ² to prepare lithographic printing plate precursors 33 to 48. .

(Protective layer coating solution 2)
・ Polyvinyl alcohol (6% by mass aqueous solution) 2.24 g
(Pura 105 manufactured by Kuraray Co., Ltd., degree of saponification: 98.5 mol%, degree of polymerization: 500)
・ Polyvinylpyrrolidone (K30) 0.0053g
-Surfactant (1% by weight aqueous solution) (Emalex 710 manufactured by Kao Corporation) 2.15 g
Scale-like synthetic mica (3.4% by mass aqueous dispersion) 3.75 g
(MEB3L manufactured by UNICOO Co., Ltd., average particle diameter of 1 to 5 μmΦ)
・ Distilled water 10.60g

(1) Exposure, development, and printing Each of the above lithographic printing plate precursors 33 to 48 was exposed with a water-cooled 40W infrared semiconductor laser-mounted Creo Trendsetter 3244VX under conditions of an output of 9 W, an outer drum rotation speed of 210 rpm, and a resolution of 2400 dpi. .
Thereafter, the aqueous solution 1 was used for the development treatment in the same manner as in Example 1 to prepare a lithographic printing plate (without heating).

On the other hand, the lithographic printing plate precursor was placed in an oven within 30 seconds after the laser exposure, and hot air was blown to heat the entire surface of the lithographic printing plate precursor, and held at 110 ° C. for 15 seconds. Thereafter, within 30 seconds, the same development treatment as described above was performed to prepare a lithographic printing plate (with heating).
Subsequently, printing durability and stain resistance were evaluated in the same manner as in Example 1 using a lithographic printing plate (without heating) and a lithographic printing plate (with heating). Comparative Example 52 was used as the evaluation standard. The results are shown in Table 4.

As is clear from the results in Table 4, the lithographic printing plate precursor according to the present invention can provide a lithographic printing plate having both high printing durability and excellent stain resistance by simple treatment.

[Examples 89 to 90 and Comparative Examples 57 to 58]
After exposing the lithographic printing plate precursors 5, 7, 37, 39 to laser images in the same manner as in Example 1 and Example 78, using the automatic development processor having the structure shown in FIG. The developer 1 having the following composition is put in the developing bath, the aqueous solution 8 having the following composition is put in the Fin bath, water is used for pre-washing and washing, and the temperature of the drying zone is 110 ° C., and the development processing is performed at a conveyance speed of 100 cm / min. The lithographic printing plate (without heating) was prepared.
On the other hand, after the laser image exposure, the same heating treatment as described above was carried out in a state where the heater of the preheating part was operated and the temperature of the preheating part was 110 ° C., and a lithographic printing plate (with heating) was prepared.
Further, the lithographic printing plate precursor supports 5, 7, 2 used for the lithographic printing plate precursors 5, 7, 37, 39 are used.
About 1 and 23, the support body which passed to the pre-washing bath, the development bath, and the Fin bath was taken out using the above developing processor, and the contact angle of each water droplet was measured.

Subsequently, printing durability and stain resistance were evaluated in the same manner as in Example 1 using a lithographic printing plate (with heating) and a lithographic printing plate (without heating). Comparative Examples 57 and 58 were used as evaluation criteria.
The results are shown in Table 5.

(Developer 1)
・ Water 100.00g
・ Benzyl alcohol 1.00g
・ Polyoxyethylene naphthyl ether (oxyethylene average number n = 13) 1.00 g
・ Dioctylsulfosuccinate sodium salt 0.50 g
・ Ethylene glycol 0.50g
・ Primary ammonium phosphate 0.05g
・ Citric acid 0.05g
・ Ethylenediaminetetraacetate tetrasodium salt 0.05g

(Aqueous solution 8)
・ Water 100.00g
・ Benzyl alcohol 1.00g
・ Dioctylsulfosuccinate sodium salt 0.50 g
・ Arabic gum 1.00g
・ Ethylene glycol 0.50g
・ Primary ammonium phosphate 0.05g
・ Citric acid 0.05g
・ Ethylenediaminetetraacetate tetrasodium salt 0.05g

  As is clear from the results in Table 5, the lithographic printing plate precursor according to the present invention combines high printing durability and excellent stain resistance even by a plate making method in which an aqueous solution containing a hydrophilizing compound is treated after development. Can be provided.

[Examples 91 to 96 and Comparative Examples 59 to 60]
For each of the lithographic printing plate precursors 33 to 40, C equipped with a water-cooled 40 W infrared semiconductor laser
Reo Trendsetter 3244VX, output 9W, outer drum rotation speed 21
The exposure was performed under the conditions of 0 rpm and resolution of 2400 dpi. The exposed lithographic printing plate precursor was attached to a cylinder of a printing machine SOR-M manufactured by Heidelberg without developing. After supplying fountain solution (1) and TRANS-G (N) black ink (manufactured by Dainippon Ink & Chemicals, Inc.) having the following composition, printing was performed at a printing speed of 6000 sheets per hour. Similarly, printing durability and stain resistance were evaluated. Comparative Example 59 was used as the evaluation standard. In addition, the aerial water droplet contact angle of the treated lithographic printing plate precursor support was measured in the same manner as in Example 78 using the following dampening solution (1) instead of the aqueous solution 1. The results are shown in Table 6.

<Dampening water (1)>
-Polymer (2) 3 parts by mass-EU-3 (Fuji Film Co., Ltd. etchant) 1 part by mass-Water 89 parts by mass-Isopropyl alcohol 7 parts by mass

As is clear from the results in Table 6, the lithographic printing plate precursor according to the present invention provides a lithographic printing plate having both high printing durability and excellent stain resistance by simple processing (on-press development). be able to.

[Examples 97 to 108 and Comparative Examples 61 to 64]
<Preparation of lithographic printing plate precursors 49-56>
An image forming layer coating solution A having the following composition is applied onto the lithographic printing plate precursor supports 17 to 24 and dried at 35 ° C. for 1 hour to form an image forming layer having a dry coating amount of 1.3 g / m ^2. Thus, lithographic printing plate precursors 49 to 56 were prepared.

(Image forming layer coating solution A)
5.83 g of carbon black in water with stirring to 11.25 g of a 10% dispersion of polymethyl methacrylate (particle diameter 90 nm) stabilized with Hostapal B (1% based on polymer) in deionized water. A 15% dispersion, 57.92 g of water and 25 g of 98% hydrolyzed polyvinyl acetate (mass average molecular weight: 200,000) 2% aqueous solution were added continuously.

<Preparation of lithographic printing plate precursors 57-64>
An image forming layer coating solution B having the following composition is applied onto the lithographic printing plate precursor supports 17 to 24 and dried at 60 ° C. for 2 minutes to form an image forming layer having a dry coating amount of 1.3 g / m ^2. Formed were lithographic printing original plates 57 to 64.

(Image forming layer coating solution B)
30 g of water
The following novolak resin fine particle dispersion 11.8 g
Tricresyl phosphate 0.1g
MegaFuck F-171 (Fluorosurfactant, 0.1g
Dainippon Ink & Chemicals, Inc.)

(Preparation of novolac resin fine particle dispersion)
12.0 g of ethyl acetate and 6.0 g of methyl ethyl ketone, 6.0 g of phenol novolac resin (meta / para ratio 60/40) having a weight average molecular weight of 1500, 1.5 g of the following photothermal conversion agent (IR-26), anionic surface activity An oil phase component was prepared by dissolving 0.1 g of an agent (Pionine A-41C (manufactured by Takemoto Oil & Fats Co., Ltd.)), and 36.0 g of 4% polyvinyl alcohol (manufactured by Kuraray Co., Ltd., PVA205) aqueous solution. The phase components were added and emulsified with a homogenizer at 15000 rpm for 15 minutes, 24.0 g of water was added, and the organic solvent was removed by heating at 40 ° C. for 3 hours.The solid content concentration of the resulting novolak resin fine particle dispersion was measured. The result was 13.0% by weight, and the average particle size was 0.25 μm.

<Exposure, development and printing>
The lithographic printing plate precursors 49 to 56 were exposed with a scanning NdYLF infrared laser emitting at 1050 nm (scanning speed 4 m / sec on the surface of the image forming layer, spot size 15 μm, output 170 mW). On the other hand, the lithographic printing plate precursors 57 to 64 were output under the conditions of an output of 9 W, an outer drum rotation speed of 210 rpm, a plate surface energy of 100 mJ / cm ² , and a resolution of 2400 dpi using a Creo Trendsetter 3244VFS equipped with a water-cooled 40 W infrared semiconductor laser. Exposed.
Thereafter, as shown in Table 7, each exposed lithographic printing plate precursor was developed and printed in the same manner as in Example 1 except that the developer 2 having the following composition was used, and evaluated in the same manner. Comparative Example 61 was used as the evaluation standard. The results are shown in Table 7.

(Developer 2)
・ Water 100.00g
・ Benzyl alcohol 1.00g
・ Polyoxyethylene naphthyl ether 1.00g
(Average number of oxyethylene n = 13)
・ Dioctylsulfosuccinate sodium salt 0.50 g
・ Arabic gum 1.00g
・ Ethylene glycol 0.50g
・ Primary ammonium phosphate 0.05g
・ Citric acid 0.05g
・ Ethylenediaminetetraacetate tetrasodium salt 0.05g

As is clear from the results in Table 7, the lithographic printing plate precursor according to the present invention having a heat-fusion type image forming layer is a lithographic printing having both high printing durability and excellent stain resistance by simple processing. A version can be provided.
[Examples 201 to 250 and Comparative Examples 201 to 248]
<Preparation of supports for lithographic printing plate precursor 1-1 to 1-7>
On the aluminum support 1 described in Example 1, a surface treatment liquid 101 having the following composition was applied and dried at 100 ° C. for 3 minutes. The coating amount of the obtained surface treatment layer was 10 mg / m ² .

(Surface treatment liquid 101)
・ Surface treatment compounds listed in Table 101 0.50 g
・ N-methylpyrrolidone 49.00g
・ Methanol 450.00g
・ Water 1.50g

The aerial water droplet contact angles of the lithographic printing plate precursors 1-1 to 1-7 thus obtained were measured according to the measurement method described above. The results are shown in Table 101.

  The lithographic printing plate precursors 1-1 to 1-7 are cut to a size of 3 × 3 cm, and 20 mL of aqueous solutions 101 to 108 having the following composition (both pH 4.5 to 5.5) are brought to a temperature of 25 ° C. Soaked for 1 minute. Thereafter, it was washed with distilled water and dried at 100 ° C. for 1 minute to obtain a support for a lithographic printing plate precursor after hydrophilization.

(Aqueous solutions 101-108)
・ Water 100.00g
・ Benzyl alcohol 1.00g
・ Polyoxyethylene naphthyl ether 1.00g
(Average number of oxyethylene n = 13)
・ Dioctylsulfosuccinate sodium salt 0.50 g
・ 3.00 g of hydrophilized compounds listed in Table 101
・ Ethylene glycol 0.50g
・ Primary ammonium phosphate 0.05g
・ Citric acid 0.05g

  The aerial water droplet contact angles of the lithographic printing plate precursor supports 1-1 to 1-7 after the hydrophilic treatment were measured in the same manner as described above. The results are shown in Table 101.

  Surface treatment compounds and hydrophilizing compounds in Table 101:

  As is clear from the results in Table 101, a large contact angle change can be obtained only when the combination of the compound having the functional group X according to the present invention and the hydrophilic compound is used. That is, the support for a lithographic printing plate precursor according to the present invention (having a compound having a functional group X on its surface) is treated with an aqueous solution containing a hydrophilizing compound (a compound having a functional group Y). The air contact angle of the surface with air drops from 70 ° to 30 °. On the other hand, when treated with an aqueous solution containing no hydrophilizing compound or when a comparative hydrophilizing compound is used, there is no or very little reduction in the contact angle of the water droplets in the air. Moreover, in the support bodies 1-6 and 1-7 which do not have the compound which has the functional group X on the surface, although an aerial water droplet contact angle is 70 degrees or more, by treatment with the aqueous solution containing a hydrophilizing compound The air contact angle of the air drops very little.

<Preparation of lithographic printing plate precursor supports 2-1 to 2-5>
A surface treatment liquid 102 having the following composition was applied on the aluminum support 1 and dried at 100 ° C. for 3 minutes. The coating amount of the obtained surface treatment layer was 10 mg / m ² .

(Surface treatment liquid 102)
・ Surface treatment compound described in Table 102 0.50 g
・ N-methylpyrrolidone 49.00g
・ Methanol 450.00g
・ Water 1.50g

  The air droplet contact angles of the lithographic printing plate precursor supports 2-1 to 2-5 and the comparative lithographic printing plate precursor supports 1-6 to 1-7 thus obtained were measured according to the measurement method described above. It was measured. The results are shown in Table 102.

  The lithographic printing plate precursor supports 2-1 to 2-5 and the comparative lithographic printing plate precursor supports 1-6 to 1-7 obtained as described above were cut to a size of 3 × 3 cm. The solution was immersed in 20 mL of an aqueous solution 109 to 116 having the following composition (all pH is 4.5-5.5) at a temperature of 25 ° C. for 1 minute. Thereafter, it was washed with distilled water and dried at 100 ° C. for 1 minute to obtain a support for a lithographic printing plate precursor after hydrophilization.

(Aqueous solutions 109 to 116)
・ Water 100.00g
・ Benzyl alcohol 1.00g
・ Polyoxyethylene naphthyl ether 1.00g
(Average number of oxyethylene n = 13)
・ Dioctylsulfosuccinate sodium salt 0.50 g
・ Hydrophilic compound described in Table 102 3.00 g
・ Ethylene glycol 0.50g
・ Primary ammonium phosphate 0.05g
・ Citric acid 0.05g

  The aerial water droplet contact angles of the lithographic printing plate precursor supports 2-1 to 2-5 and the comparative lithographic printing plate precursor supports 1-6 to 1-7 after the hydrophilization treatment were measured in the same manner as described above. The results are shown in Table 102.

  Surface treatment compounds and hydrophilizing compounds in Table 102:

  As is clear from the results in Table 102, a large contact angle change can be obtained only when the combination of the compound having the functional group X according to the present invention and the hydrophilic compound is used. That is, the support for a lithographic printing plate precursor according to the present invention (having a compound having a functional group X on its surface) is treated with an aqueous solution containing a hydrophilizing compound (a compound having a functional group Y). The air contact angle of the surface with air drops from 70 ° to 30 °. On the other hand, when treated with an aqueous solution containing no hydrophilizing compound or when a comparative hydrophilizing compound is used, there is no or very little reduction in the contact angle of the water droplets in the air. Moreover, in the support bodies 1-6 and 1-7 which do not have the compound which has the functional group X on the surface, although an aerial water droplet contact angle is 70 degrees or more, by treatment with the aqueous solution containing a hydrophilizing compound The air contact angle of the air drops very little.

<Preparation of planographic printing plate precursors 1-1 to 1-12>
The photosensitive layer and the protective layer were applied to the above lithographic printing plate precursor supports in the same manner as in Example 1 to prepare lithographic printing plate precursors 1-1 to 1-12. However, the dry coating amount of the protective layer was changed to 0.50 g / m ² .

(1) Exposure, development and printing Each of the above lithographic printing plate precursors 1-1 to 1-12 is subjected to laser image-like exposure in the same manner as in Example 1, and then the aqueous solutions 101 to 107 as shown in Table 103. Alternatively, using the aqueous solutions 109 to 115, development processing was carried out in the same manner as in Example 1 using an automatic development processor having the structure shown in FIG. 1 to prepare a lithographic printing plate (without heating).

On the other hand, the lithographic printing plate precursor was placed in an oven within 30 seconds after the laser image-like exposure, and the entire surface of the lithographic printing plate precursor was heated by blowing hot air, and kept at 110 ° C. for 15 seconds. Thereafter, within 30 seconds, the same development treatment as described above was performed to prepare a lithographic printing plate (with heating).
Next, printing was performed in the same manner as in Example 1 using a lithographic printing plate (without heating) and a lithographic printing plate (with heating).

(2) Evaluation Evaluation of printing durability and stain resistance was carried out in the same manner as in Example 1. The results are shown in Table 103. However, as a standard (100) for relative evaluation, a comparative example described as “evaluation standard” in Table 103 was used.

  As is apparent from the results in Table 103, the lithographic printing plate produced from the lithographic printing plate precursor according to the present invention can improve stain resistance while maintaining good printing durability.

[Examples 251 to 270 and Comparative Examples 249 to 284]
<Preparation of lithographic printing plate precursor 1-13 to 1-18>
The photosensitive layer coating solution 2 described in Example 17 was applied on the lithographic printing plate precursor supports 1-1, 1-3, 1-6, 1-7, 2-1, and 2-3, and 80 Dry at 1 ° C. for 1 minute. The coating amount of the obtained photosensitive layer was 1.2 g / m ² .

On the photosensitive layer, a protective layer coating solution 3 having the following composition was applied using a bar so that the dry coating amount was 0.50 g / m ^2, and then dried at 125 ° C. for 70 seconds to form a protective layer. Then, lithographic printing plate precursors 1-13 to 1-18 were prepared.

(Protective layer coating solution 3)
・ The following mica dispersion (1): 13.00 g
Polyvinyl alcohol (saponification degree 98 mol%, polymerization degree 500) 1.30 g
-Sodium 2-ethylhexyl sulfosuccinate 0.20 g
・ Poly (vinyl pyrrolidone / vinyl acetate = 1/1) (molecular weight 70,000) 0.05g
・ Surfactant (Emalex 710, manufactured by Nippon Emulsion Co., Ltd.) 0.05g
・ Water 133.00g

(Preparation of mica dispersion (1))
To 368 g of water, 32 g of synthetic mica (“Somasif ME-100”: manufactured by Corp Chemical Co., aspect ratio: 1000 or more) was added, and dispersed using an homogenizer until the average particle size (laser scattering method) became 0.5 μm. A mica dispersion (1) was obtained.

  The obtained lithographic printing plate precursors 1-13 to 1-18 were exposed, developed and printed in the same manner as in Example 201 using each aqueous solution as shown in Table 104, and evaluated in the same manner. The results are shown in Table 104. However, as a standard (100) for relative evaluation, a comparative example described as “evaluation standard” in Table 104 was used.

  As is apparent from the results in Table 104, the lithographic printing plate produced from the lithographic printing plate precursor according to the present invention can improve stain resistance while maintaining good printing durability.

[Examples 271 to 280 and Comparative Examples 285 to 290]
A surface treatment liquid 103 having the following composition was applied on the aluminum support 2 described in Example 78 and dried at 100 ° C. for 3 minutes to prepare a support 3-1 for a lithographic printing plate precursor. The coating amount of the obtained surface treatment layer was 7 mg / m ² .

(Surface treatment liquid 103)
・ Surface treatment compound (3) 0.50 g
・ N-methylpyrrolidone 50.00g
・ Methanol 450.00g

On the aluminum support 2 described in Example 78, a surface treatment coating solution 104 having the following composition was applied and dried at 100 ° C. for 3 minutes to prepare a support 3-2 for a lithographic printing plate precursor. The coating amount of the obtained surface treatment layer was 8 mg / m ² .

(Surface treatment liquid 104)
-0.50g of the above surface treatment compound (10)
・ N-methylpyrrolidone 50.00g
・ Methanol 450.00g

<Preparation of planographic printing plate precursors 1-19 and 1-20>
The photosensitive layer coating solution 3 described in Example 78 was bar-coated on the lithographic printing plate precursor supports 3-1 and 3-2, and then oven-dried at 70 ° C. for 60 seconds. A photosensitive layer of 1 g / m ² was formed.

On the photosensitive layer, the protective layer coating solution 2 described in Example 78 was coated with a bar and then oven-dried at 125 ° C. for 75 seconds to form a protective layer having a dry coating amount of 0.15 g / m ^2. Printing plate precursors 1-19 and 1-20 were prepared.

  Each of the above-described lithographic printing plate precursors 1-19 and 1-20 was exposed with a Trendsetter 3244VX manufactured by Creo equipped with a water-cooled 40 W infrared semiconductor laser under the conditions of an output of 9 W, an outer drum rotating speed of 210 rpm, and a resolution of 2400 dpi.

  Thereafter, as shown in Table 105, development and printing were performed in the same manner as in Example 201 except that an aqueous solution 117-131 having the following composition was used. Further, with respect to the lithographic printing plate precursor supports 3-1 and 3-2, the air water droplet contact angles before and after the treatment with the hydrophilizing compound were measured in the same manner as in Example 201. The results are shown in Table 105. However, as a standard (100) for relative evaluation, a comparative example described as “evaluation standard” in Table 105 was used.

(Aqueous solutions 117 to 131)
・ Water 100.00g
・ Polyoxyethylene naphthyl ether 0.50g
(Average number of oxyethylene n = 13)
・ Dioctylsulfosuccinate sodium salt 0.50 g
・ 3.00 g of hydrophilized compounds described in Table 105
・ Primary ammonium phosphate 0.05g
・ Citric acid 0.05g

  As is apparent from the results in Table 105, the lithographic printing plate produced from the lithographic printing plate precursor according to the present invention can improve stain resistance while maintaining good printing durability.

[Examples 281 to 290 and Comparative Examples 291 to 296]
<Preparation of lithographic printing plate precursor 1-21>
An image forming layer coating solution C having the following composition is bar-coated on the lithographic printing plate precursor support 3-1, and then oven-dried at 100 ° C. for 120 seconds to obtain an image having a dry coating amount of 1.1 g / m ² . A forming layer was formed to prepare a lithographic printing plate precursor 1-21.

(Image forming layer coating solution C)
・ The following thermal decarboxylation polymer (1) 1.0 g
・ Infrared absorber NK-3508 0.15g
(Nippon Sensitive Dye Research Institute)
・ Megafuck F-177 0.06g
(Dainippon Ink & Chemicals, Fluorosurfactant)
・ Methyl ethyl ketone 20 g
・ Methyl alcohol 7 g

Thermal decarboxylation polymer (1)

<Preparation of lithographic printing plate precursor 1-22>
An image forming layer coating solution D having the following composition is bar-coated on the lithographic printing plate precursor support 3-2, followed by oven drying at 80 ° C. for 180 seconds, and an image having a dry coating amount of 1.2 g / m ² . A forming layer was formed to prepare a lithographic printing plate precursor 1-22.

(Image forming layer coating solution D)
-4.0 g of the following thermosensitive polymer compound (1)
・ Infrared absorber (IR-125, manufactured by Wako Pure Chemical Industries, Ltd.) 0.15 g
・ Acid generator 0.15g
Diphenyliodonium anthraquinone sulfonate
・ 0.05g of counter ion of Victoria Pure Blue BOH
1-naphthalene-sulfonic acid dye
・ Fluorine surfactant 0.06g
(Megafuck F-177 manufactured by Dainippon Ink & Chemicals, Inc.)
・ Methyl ethyl ketone 20g
・ Γ-Butyrolactone 10g
・ 8g of 1-methoxy-2-propanol
・ Water 2g

Thermosensitive polymer compound (1)

  The resulting lithographic printing plate precursors 1-21 and 1-22 were subjected to image exposure, development and printing in the same manner as in Example 271 using an aqueous solution 117-131 as shown in Table 106. And soil resistance were evaluated. The results are shown in Table 106. However, as a standard (100) for relative evaluation, a comparative example described as “evaluation standard” in Table 106 was used.

  As is apparent from the results in Table 106, the lithographic printing plate precursor according to the present invention having a polarity conversion type image forming layer can improve stain resistance while maintaining good printing durability.

[Examples 291 to 300 and Comparative Examples 297 to 300]
After exposing the lithographic printing plate precursors 1-1 and 1-17 to laser images in the same manner as in Example 201 and Example 261, using the automatic development processor having the structure shown in FIG. A developer 1-1 having the following composition is placed in a developing bath, an aqueous solution 132-145 having the following composition is placed in a Fin bath, water is used for pre-water washing and water washing, the temperature of the drying zone is 110 ° C., and the conveyance speed is 100 cm / The development process was performed in minutes, and a lithographic printing plate (no heating) was prepared.
On the other hand, after the laser image exposure, the same heating treatment as described above was carried out in a state where the heater of the preheating portion was operated and the temperature of the preheating portion was 110 ° C. to prepare a lithographic printing plate (with heating).

  Subsequently, printing durability and stain resistance were evaluated in the same manner as in Example 201 using a lithographic printing plate (with heating) and a lithographic printing plate (without heating). The results are shown in Table 107. However, as a standard (100) for relative evaluation, a comparative example described as “evaluation standard” in Table 107 was used.

(Developer 1-1)
・ Water 100.00g
・ Benzyl alcohol 1.00g
・ Polyoxyethylene naphthyl ether 1.00g
(Average number of oxyethylene n = 13)
・ Dioctylsulfosuccinate sodium salt 0.50 g
・ Ethylene glycol 0.50g
・ Primary ammonium phosphate 0.05g
・ Citric acid 0.05g

(Aqueous solution 132-145)
・ Water 100.00g
・ Dioctylsulfosuccinate sodium salt 0.50 g
・ Hydrophilic compounds listed in Table 7 2.00 g
・ Primary ammonium phosphate 0.05g
・ Citric acid 0.05g

  As is apparent from the results in Table 107, the lithographic printing plate precursor according to the present invention has improved stain resistance while maintaining good printing durability even by a plate making method in which an aqueous solution containing a hydrophilizing compound is treated after development. Lithographic printing plates can be provided.

[Examples 301 to 320 and Comparative examples 301 to 312]
Each of the lithographic printing plate precursors 1-19 to 1-22 was exposed under the conditions of an output of 9 W, an outer drum rotating speed of 210 rpm, and a resolution of 2400 dpi using a Trend setter 3244VX manufactured by Creo equipped with a water-cooled 40 W infrared semiconductor laser. The obtained exposed lithographic printing plate precursor was mounted on a cylinder of a printing machine SOR-M manufactured by Heidelberg without developing. After supplying fountain solutions (1-1) to (1-15) and TRANS-G (N) black ink (manufactured by Dainippon Ink & Chemicals, Inc.) having the composition shown below, the printing speed was 6000 sheets per hour. Printing was performed, and printing durability and stain resistance were evaluated in the same manner as in Example 201. The results are shown in Table 108. However, as a standard (100) for relative evaluation, a comparative example described as “evaluation standard” in Table 108 was used.

<Dampening water (1-1) to (1-15)>
-3 parts by mass of the hydrophilized compounds listed in Table 108-EU-3 (Etchi liquid manufactured by Fuji Film Co., Ltd.) 1 part by mass-89 parts by mass of water-7 parts by mass of isopropyl alcohol

  As is clear from the results in Table 108, the lithographic printing plate precursor according to the present invention provides a lithographic printing plate having both high printing durability and excellent stain resistance by simple processing (on-press development). be able to.

[Examples 321 to 330 Comparative Examples 313 to 318]
<Preparation of lithographic printing plate precursor 1-23>
The image forming layer coating solution A is applied onto the lithographic printing plate precursor support 3-1, and dried at 35 ° C. for 1 hour to form an image forming layer having a dry coating amount of 1.3 g / m ^2. A lithographic printing plate precursor 1-23 was produced.

<Preparation of lithographic printing plate precursor 1-24>
The image forming layer coating solution B is coated on the lithographic printing plate precursor support 3-2 and dried at 60 ° C. for 2 minutes to form an image forming layer having a dry coating amount of 1.3 g / m ^2. A lithographic printing plate precursor 1-24 was prepared.

<Exposure, development and printing>
The lithographic printing plate precursor 1-23 was exposed with a scanning NdYLF infrared laser emitting at 1050 nm (scanning speed 4 m / sec on the surface of the image forming layer, spot size 15 μm, output 170 mW). On the other hand, the lithographic printing plate precursor 1-24 was subjected to a Creo Trendsetter 3244VFS equipped with a water-cooled 40 W infrared semiconductor laser under the conditions of an output of 9 W, outer drum rotation speed of 210 rpm, plate surface energy of 100 mJ / cm ² and resolution of 2400 dpi. Exposed.
Thereafter, as shown in Table 109, each exposed lithographic printing plate precursor was developed and printed in the same manner as in Example 201 except that the aqueous solution 117-131 was used, and evaluated in the same manner. The results are shown in Table 109. However, as a standard (100) for relative evaluation, a comparative example described as “evaluation standard” in Table 109 was used.

  As is clear from the results in Table 109, the lithographic printing plate precursor according to the present invention having a heat-fusion type image forming layer is a lithographic printing having both high printing durability and excellent stain resistance by simple processing. A version can be provided.

It is explanatory drawing which shows the structure of an automatic developing processor. It is explanatory drawing which shows the structure of another automatic developing processor.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Conveying roller pair 2 Conveying roller pair 3 Rotating brush roller 4 Conveying roller pair 5 Conveying roller pair 6 Rotating brush roller 7 Rotating brush roller 8 Conveying roller pair 9 Conveying roller pair 10 Receiving roller 11 Conveying roller pair 12 Conveying roller pair 13 Conveying roller Pair 61 Rotating brush roll 62 Receiving roll 63 Conveying roll 64 Conveying guide plate 65 Spray pipe 66 Pipe line 67 Filter 68 Plate feeding table 69 Plate discharging table 70 Developer tank 71 Circulating pump 72 Plate

Claims (14)

  In a lithographic printing plate precursor comprising a support having a surface with a water droplet contact angle of 70 ° or more and a photosensitive layer, the support has a compound having a functional group X on the surface, the functional group X being By contacting with a compound having a functional group Y capable of interacting with the compound having the functional group Y to form a chemical bond with the compound having the functional group Y and adsorbing the compound having the functional group Y to the support surface, A lithographic printing plate precursor characterized by being a functional group capable of lowering the contact angle of water droplets on the surface of a support to 30 ° or less. The lithographic printing plate precursor as claimed in claim 1, wherein the functional group X is a functional group represented by the following general formula (0).
In the formula, R _{1 to} R ₃ each independently represents a monovalent substituent or a covalent bond composed of at least one atom selected from hydrogen, carbon, oxygen, nitrogen, sulfur, phosphorus, halogen, and silicon; Any two or more may be bonded to each other to form a ring. However, at least one of R _{1 to} R ₃ is a divalent linking group linked to a compound nucleus, which is composed of at least one atom selected from hydrogen, carbon, oxygen, nitrogen, sulfur, phosphorus, halogen and silicon. Represents. The functional group Y is —COOH, —SO ₃ H, —PO (OH) (OM) and —B (OH).
The lithographic printing plate precursor as claimed in claim 1 or 2, wherein (OM) is a functional group selected from hydrogen, metal cation, ammonium, phosphonium, iodonium, sulfonium, diazonium or azinium. .   2. The lithographic printing plate precursor according to claim 1, wherein the functional group X is a functional group having a positive charge, and the functional group Y is a functional group having a negative charge. The functional group X is a functional group represented by the following general formulas (1) to (5), and the functional group Y is a functional group represented by the following general formulas (6) to (8). The lithographic printing plate precursor as claimed in claim 4, wherein the lithographic printing plate precursor is provided.
In the formula, R _{1 to} R ₃ each independently represent hydrogen, an alkyl group, an aryl group, an alkenyl group, or an alkynyl group, L represents a divalent linking group linked to the compound mother nucleus, and Z ⁻ represents a pair Represents an anion.
In the formula, M1 ⁺ and M2 ⁺ each independently represent a counter cation, and L represents a divalent linking group linked to the compound mother nucleus.   The lithographic printing plate precursor as claimed in claim 1, wherein the functional group X is a functional group having a negative charge, and the functional group Y is a functional group having a positive charge. The functional group X is a functional group represented by the following general formulas (9) to (11), and the functional group Y is a functional group represented by the following general formulas (12) to (16). The lithographic printing plate precursor as claimed in claim 6, wherein the lithographic printing plate precursor is provided.
In the formula, M1 ⁺ and M2 ⁺ each independently represent a counter cation, and L represents a divalent linking group linked to the compound mother nucleus.
In the formula, R _{1 to} R ₃ each independently represent hydrogen, an alkyl group, an aryl group, an alkenyl group, or an alkynyl group, L represents a divalent linking group linked to the compound mother nucleus, and Z ⁻ represents a pair Represents an anion. The lithographic printing plate precursor as claimed in any one of claims 1 to 7, wherein the photosensitive layer contains a binder polymer having an acid value of 0.3 mmol / g or less. The lithographic printing plate precursor as claimed in claim 1, wherein the photosensitive layer contains a sensitizing dye having absorption at 350 to 1200 nm.   The lithographic printing plate precursor as claimed in claim 1, further comprising a protective layer on the photosensitive layer.   In the preparation method of the lithographic printing plate which develops the lithographic printing plate precursor according to any one of claims 1 to 10 with an aqueous solution having a pH of 2 to 10 to form a non-image portion after image exposure, A method for preparing a lithographic printing plate, comprising: after development, treating with an aqueous solution containing the compound having the functional group Y to reduce the contact angle of airborne water droplets on the support surface in an unexposed area to 30 ° or less.   The lithographic printing plate precursor according to any one of claims 1 to 10 is image-exposed with a laser having an oscillation wavelength of 350 to 1200 nm, and then the pH containing the compound having the functional group Y is 2 to 10 A method for preparing a lithographic printing plate, comprising developing with an aqueous solution to remove a photosensitive layer in a non-exposed portion to form a non-image portion surface having a contact angle of water droplets of 30 ° or less.   The lithographic printing plate precursor according to any one of claims 1 to 10 is image-exposed with a laser having an oscillation wavelength of 350 to 1200 nm and developed with an aqueous solution having a pH of 2 to 10 to form a photosensitive layer in an unexposed area. Is removed, and then treated with an aqueous solution containing the compound having the functional group Y and having a pH of 2 to 10 to form a non-image part surface having an airborne water droplet contact angle of 30 ° or less. Manufacturing method. The method for producing a lithographic printing plate as claimed in any one of claims 11 to 13, wherein the exposed lithographic printing plate precursor is subjected to a heat treatment between the image exposure and development.