TW200819915A - Photosensitive composition, image recording material including the composition, and method for producing lithographic printing plate - Google Patents

Abstract

This invention provides a photosensitive composition, an image recording material thereof, and a method for manufacturing a planographic printing plate, wherein the photosensitive composition has high sensitivity to oscillation wavelength of the shorter wavelength semiconductor laser and has excellent stability for storage. The photosensitive composition comprises (A) a diimidazole compound, (B) a photosensitive dye having absorption for λ max at wavelength of 350 nm - 850 nm, and (C) polymeric compounds.

Description

200819915 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a method of making a lithographic printing plate. In particular, there is a photosensitive composition for treating a lithographic printing plate of a lithographic printing plate precursor using a developing solution, an image recording material using the same, an image recording method, a lithographic printing plate, and a method for producing the same, which are short for the photosensitive composition The wavelength semiconductor laser has high sensitivity, excellent storage stability, and excellent safety light suitability. [Prior Art] Previously, lithographic printing plate precursors have been widely used in the ps plate, which has a structure in which a lipophilic photosensitive resin layer is provided on a hydrophilic support, and the plate making method is usually high in transmission. Contrast lith film After reticle exposure (surface exposure), a desired printing plate is obtained by dissolving and removing the non-image portion. In recent years, digital technology that uses computers to electronically process, accumulate, and output image information has been widely used, and various corresponding new image output methods have been put into practical use. As a result, it is expected that a computer-to-plate (CTP) technology capable of directly producing a printing plate by scanning digital information such as laser light with high directivity can be directly scanned without using a high-contrast photosensitive film. And how to get the original version of the printing plate adapted to this technology has become an important issue. One of the ways of obtaining such a lithographic printing plate capable of scanning exposure can be a method of forming an ink receptive resin layer region on a support having a hydrophilic surface. There is a proposal to reveal a structure, and there is also a material that has been used in 200819915. It is a material in which a negative photosensitive layer is provided on a support to describe the hardening to form an ink receiving region, and the photosensitive speed is excellent. Photopolymerizable composition. The brush-type original plate of such a structure is easy to develop, and has excellent resolution, good brushing property, and good stain resistance. The photopolymerizable composition basically contains an ethylenic bond. The polymerizable compound, the photopolymerization initiator, and the resin as needed are subjected to scanning exposure, and the photoinitiator absorbs light, generates an active species such as a living group, and generates a polymerization reaction of the polymerizable compound, thereby hardening the domain to form an image. . In such a photopolymerizable composition capable of scanning and exposing, a photoinitiator having excellent photosensitivity is disclosed (see, for example, Patent Documents 1 and 2). The light-inducing system described is applied to a CTP system before long-wavelength visible light using an extended light source such as Ar Reynolds or FD-YAG laser (53 2 nm), and the output of the current light source is insufficient. Unsensible sensitivity, I hope to have a highly sensitive hairline that can be adapted for higher speed exposure. On the other hand, in recent years, for example, an InGaN-based material has been used, and a semiconductor laser which can continuously oscillate in a region of nanometer to 450 nm has been used. A scanning exposure system using such short-wave light has the advantage of being able to construct a sufficiently economical system because the semiconductor structure can be manufactured inexpensively. Moreover, when compared with a system using the previous FD-YAG laser, it is possible to use a lithographic printing plate precursor which is photosensitive in a brighter safety industry and which is photosensitive at a short wavelength. However, by sweeping, the lithographic and anti-saturated adhesive free exposure areas show various such shots (the 488 source is first obtained with a charge at 3 50 to reach the solid laser output, or under Ar light. It is not known at this time that the light-inducing system with sufficient sensitivity to scanning exposure in the short-wavelength region of 305 nm to 450 nm is not known in this case. In view of the above situation, although the applicant of the case has previously proposed (for example Referring to Patent Document 1), a photosensitive composition containing a sensitizing colorant in the short-wavelength region is disclosed, but it is desirable that such a photoinitiator containing a sensitizing colorant can be more highly sensitive. Moreover, for example, a non-patent As described in documents 3 and 4, it is still a desirable technique to obtain a highly sensitive photoinitiator in a wide field of imaging. A photoinitiator consisting of a sensitizing colorant and an initiator can be produced by selecting an initiator. In addition to active radicals, acids and bases can also be produced. For example, it can be used in the field of electronic materials such as image formation, holographic imaging, color hard copying, or optical resistance. Use of photocurable resin materials such as inks, paints, and adhesives. In these industrial fields, in order to efficiently decompose the initiator, it is desired to find a sensitizing colorant having excellent light absorption and sensitization properties. The lithographic printing plate precursor of the photosensitive layer composed of the photopolymerizable composition is excellent in high sensitivity and excellent in preservability, and in recent years, the components in the photosensitive layer are not subjected to the development processing step. Precipitation (no imaging gas) becomes important. In addition to the previous alkali imaging (pH 10 to 14), there are also proposals to disclose a plate making method using a developing solution having a pH of 2 to 10. That is, no It is only a subject of high sensitivity, preservation stability, and good development of the lithographic printing plate, and a new technology is required. [Patent Document 1] JP-A-2004-3 09977 [Non-Patent Document 1] B ruee Μ · Μ ο nr 〇e et al., Chemical Begging 200819915 (Chemical Reviews), 93, 43 5 (19 9 3) [Non-Patent Document 2] R. S. Davidson, Photochemistry and Biology A Journal: Chemistry (J 〇urna 1 〇f P h 〇t 〇 chemistry and B i ο 1 〇 gy A : Chemistry), 73, 81 (1993) [Non-Patent Document 3] P. Faussier, Principle and Application of Photoinitiated Polymers (Photoinitiated Polymerization-Theory And Applica tions), Rapra Review vol.9, Report P apra Technology (19 9 8) [Non-Patent Document 4] Μ. Tsunooka et al. 'Prog. Polym. Sci., _ 21, 1 (1996) [Problem to be Solved by the Invention] An object of the present invention is to provide a photosensitive composition for lithography, an image recording material using the composition, an image recording method, a lithographic printing plate, and a lithographic printing plate. The photosensitive composition for lithography has high sensitivity especially for an oscillation wavelength of 350 nm to 45 nm of an inexpensive short-wavelength semiconductor laser, for example, for scanning exposure suitable for a CPT system. The original version of the lithographic printing plate has excellent workability and development (no imaging gas). [Means for Solving the Problem] In order to achieve the above object, the inventors of the present invention have found that a novel photoinitiator containing a diimidazole type compound having a specific structure represented by the general formula (I) can impart high sensitivity by repeating the results of intensive discussion. In particular, it has high sensitivity and excellent imaging properties in the vicinity of 305 nm to 450 nm, and the present invention was completed in 200819915. That is, the present invention is as follows.感光] a photosensitive composition comprising (A) a diimidazole-type compound having a structure represented by the following formula (I), and (B) having a sensitization of an absorption maximum wavelength λ ma X at 350 nm to 850 nm Colorant, and (C) polymerizable compound,

(In the formula (I), Ri to R6 represent any one of a aryl group which may have a substituent, and a heteroaryl group which may have a substituent, and at least two of R! to R6 have a group selected from a COOR7 group, An aryl or heteroaryl group of a substituent of a SO3R8 group, a PO3R9 group, an OH group, and an OCORio group, and R7 to R1G each independently represent a valence group of a non-hydrogen atom). [2] The photosensitive composition according to [1], wherein the sensitizing colorant (B) is selected from the group consisting of a coumarin coloring material, a styrene-based coloring material, an anthocyanin coloring material, and a merocyanine coloring material. [3] An image recording material which is provided on a support and which has a photosensitive layer containing a photosensitive composition such as [1] or [2]. [4] An image recording method using a laser light source having a wavelength shorter than 405 nm to have a photosensitive layer containing a photosensitive composition such as any one of [1] to [3] on a support The image recording material is scanned and exposed. [5] A lithographic printing plate is attached to a support and has a photosensitive layer containing a photosensitive composition such as [1] or [2]. [6] A method for producing a lithographic printing plate, characterized in that the method comprises the following steps: the lithographic printing plate precursor having a support, a photosensitive layer and a protective layer in the following order according to the following sequence, at a wavelength of 3 5 0 to 4 50 After the laser exposure of the meter, the photosensitive layer of the protective layer and the non-exposed portion is removed in the presence of a developing solution having a pH of 10 to 14; wherein the photosensitive layer contains (A) a structure having the structure represented by the following formula (1) An imidazole-type compound, (B) a sensitized colorant having a maximum absorption wavelength λ max of from 350 nm to 850 nm, (C) a polymerizable compound, and (D-1) an alkali-soluble binder polymer,

(In the formula (I), Ri to R6 represent any one of an aryl group which may have a substituent and a heteroaryl group which may have a substituent, and at least two of R^ to R6 have a group selected from a COOR7 group. An aryl or heteroaryl group of a substituent of a S03R8 group, a PO3R9 group, an OH group, and an OCOR10 group, and R7 to Rio each independently represent a valence group of a non-hydrogen atom). v [7] A method for producing a lithographic printing plate, characterized in that it comprises the following steps: a lithographic printing plate precursor having a support, a photosensitive layer, and a protective layer in the following order, at a wavelength of 3,500 to 450 nm After exposure, the photosensitive layer of the protective layer and the non-exposed portion is removed in the presence of a developing solution having a pH of 2 to 10; wherein the photosensitive layer contains (A) a diimidazole having a structure represented by the following formula (I) a compound of the type (B) having a sensitizing colorant having an absorption maximum wavelength λ max of from 3 50 nm to 8 50 nm, (C) a polymerizable compound, and (D-2) an acid value of 0.3 meq/g or less Hydrophobic Adhesive Polymer, -10- 200819915

(In the formula (I), it represents any one of an aryl group which may have a substituent and a heteroaryl group which may have a substituent, and at least two of them have a group selected from a COOR7 group, a S03R8 group, a P03R9 group, and a fluorene group. The H group and the aryl or heteroaryl group of the substituent of the OCOR10 group, and R7 to R!o each independently represent a valence group of a non-hydrogen atom). The mechanism of action of the present invention is not clear, and the diimidazole-type compound represented by the above formula (1) has an absorption maximum wavelength λ max with respect to 3 5 〇 nm to 850 nm, particularly at 3 50 Meters ~450 nm have high sensitivity when combined with sensitized colorants that absorb the maximum wavelength λ max . This is because the sensitized colorant has an electron-excited state with high sensitivity to the irradiation (exposure) of the oscillation wavelength of the inexpensive short-wavelength semiconductor laser, and the electron absorption related to the electronic excitation state by the light absorption, Energy transfer, heat generation, and the like act on a diimidazole type compound represented by the formula (1) to cause a chemical change to generate a radical, an acid or a base. Further, at least one of the radicals, acids or bases produced herein can cause irreversible changes such as coloration, color reduction, and polymerization of the polymerizable compound to be reacted. Among such compounds, an addition polymerizable compound having an ethylenically unsaturated double bond is preferably used to initiate a curing reaction, and to cure the exposed region. Therefore, by using the photosensitive composition of the present invention, it has sufficient sensitivity to scanning exposure of a short-wavelength semiconductor laser, and is excellent in safety under a yellow light, and can also be safe in a bright -11-200819915. The advantages of light processing. Therefore, it is considered that the lithographic printing plate precursor which is obtained by using the additive composition containing the addition polymerizable compound as the photosensitive layer is capable of recording with high sensitivity and exhibiting printing performance excellent in safety light stability. . Further, the photosensitive composition of the present invention (containing a diimidazole type compound having a specific structure) is excellent in developability. It is considered that the important factor is that there are hydrophilic substituents (OH, OCOR, COOR, etc.) in the vicinity of the sensitized colorant structure, and it is needless to say that the alkali developing solution is also possible because the high solubility can be maintained in the aqueous solution in the weakly acidic region. Therefore, it is possible to suppress the deposition of coloring materials and the generation of gas, and to bring about an effect of improving the developing property. [Effects of the Invention] According to the lithographic printing plate of the present invention, the oscillation wavelength of the inexpensive short wavelength of from 350 nm to 45 nm is particularly high in sensitivity and excellent in storage stability, for example, Provide scanning exposure for CPT system - industry ^ ^ imaging ^ degree · excellent - _ _ _ _ print _ original version __ version ^-------------- [Embodiment] Hereinafter, the present invention will be described in detail. The photosensitive composition of the present invention is characterized in that it contains the following components (A) to (C), (A) a diimidazole-type compound having a structure represented by the formula (I), and (B) at 350 nm to 850 nm. The rice has a sensitizing color absorbing the maximum wavelength λ max , and (C) a polymerizable compound. Further, the preferred lithographic printing plate precursor of the present invention has a support of -12-200819915 in the following order, a photosensitive layer (containing a (II) diimidazole type compound having a structure represented by the following formula (I), (B) at 3 50 nm to 850 nm having a sensitizing color absorbing material having a maximum wavelength λ ma>, (C) a polymerizable compound, and (D) an alkali-soluble binder polymer, or a hydrophobic acid having an acid value of 0.3 meq/g or less Adhesive polymer), and protective layer. Each component contained in the photosensitive composition of the present invention will be described in detail below. (A) a diimidazole type compound having a structure represented by the following formula (I),

(In the formula (I), Ri to R6 represent any one of an aryl group which may have a substituent and a heteroaryl group which may have a substituent, and at least two of Ri to R6 have a selected from the group consisting of COOR7 group and S03R8. An aryl or heteroaryl group of a substituent of a P03R9 group, an OH group, and an OCORio group, and R7 to R1() each independently represent a valence group of a non-hydrogen atom). A diimidazole type compound having a structure represented by the general formula (I) (hereinafter referred to as a diimidazole type compound or a specific initiator of the present invention) having a hydrophilicity and a combination in an alkali developing solution The solubility in the soluble/weakly acidic aqueous solution does not produce a significant feature of the imaging gas in the development step. The amount of the diimidazole-type compound of the present invention dissolved in a developing solution at 25 ° C (adjusted to an aqueous solution of pH = 4.5 or 11.95) is preferably 1 〇〇 (mg / liter) or more. The amount of dissolution is preferably 200 or more (mg/L) or more, more preferably -13 to 200819915 3 00 (mg/L) or more. When the amount of dissolution in a developing solution at 25 ° C (adjusted to an aqueous solution of ρ Η = 4.5) is 1 〇〇 (mg / liter) or more, the substituent is hydrolyzable, An ester group or the like and a hydroxyl group are preferred. When the amount of dissolution in a developing solution at 25 ° C (adjusted to an aqueous solution of ρ Η = 1. 1.95) is 1 〇〇 (mg / liter) or more, the substituent is preferably a non-hydrolyzable group, and a hydroxy group is used. It is better. The amount of the diimidazole-type compound of the present invention dissolved in an aqueous alkali solution (ΡΗ = 1 1.95) and the amount dissolved in a weak acid aqueous solution (ρ Η = 4.5) can be determined as follows. The aqueous solution of the predetermined pH is a developing solution at 25 ° C (adjusted to an aqueous solution of ρ Η = 11.95). The additives to be used include hydrazine, NaOH, K2C03, and KHC03. The base of the present invention is not limited thereto, and all of them can adjust the p Η of the aqueous solution to 1.0 to 1 4.0. A weakly acidic aqueous solution having a predetermined pH is a developing solution at 25 ° C (an aqueous solution adjusted to pH = 4.5). Examples of the additive to be used include phosphoric acid, citric acid, EDTA4Na salt, and sulfonate. The weak acidity of the present invention is not limited thereto, and all of them can adjust the pH of the aqueous solution to 2.0 to 10.0. In the present invention, the combination of (A) a specific initiator and (B) a sensitized colorant having a maximum absorption wavelength λ max at 350 to 850 nm exhibits high photodegradation efficiency, And very high sensitivity. In general, it is known that a sensitization mechanism of a photoinitiator composed of a sensitizing colorant/initiator is via the following path, (a) based on electrons from the electronically excited state of the sensitized toner to the source - 14-200819915 Reacting, the initiator produces reductive decomposition; (b) based on the movement of electrons from the initiator to the electronically excited state of the sensitizing toner, the initiator is oxidatively decomposed; and (C) based on the energy from the electronically excited state of the sensitizing toner The agent shifts the initiator to decompose from the electronically excited state; it is known that the specific initiator of the present invention can cause the sensitization reaction of any of these types with excellent efficiency. Further, the important factor of the specific initiator of the present invention is that high-efficiency colorant fluorescent extinction (fluorescence and/or phosphorescence) is considered to be a specific initiator of the present invention which may have the above partial structure. The color reaction efficiency of the sensitized colorant may be high. Other possibilities are that the partial structure represented by the general formula (I) is efficient in the initial stage of the sensitization reaction (electron movement, etc.), and it is also possible that the decomposition of the initiator is achieved to contribute to the efficiency of the subsequent reaction. The specific initiator used in the present invention is considered to be because the aryl or heteroaryl group of Ri to R6 has a hydrophilic substituent such as a COOR2 group, a S03R3 group, a PO3R4 group, a 0η group, and an OCOR5 group. The weak acid/alkaline aqueous solution having a water pH of 2 to 7, or 10 to 14 has a high affinity, which contributes to suppressing the coloring of the coloring material to generate a gas and improve the developability. Further, the specific initiator represented by the formula (I) is preferably a structure represented by the following formula (11).

• 15-200819915 In the formula (II), m and η are selected from an integer of 〇~4, and R11 to R16 represent a hydrogen atom or a monovalent non-metal atomic group. Wherein at least two of Rh to R16 are selected from the group consisting of a C00r2 group, an S〇3R3 group, a P03R4 group, an OH group, and a ruthenium COR5 group (here, r2, R4 and R5 are each independently monovalent) Non-metal atomic group). Namely, in the structure represented by the formula (II), at least two benzene rings (having an auricular group selected from the group consisting of a COOR2 group, a SO3R3 group, a PO3R4 group, an OH group, and a 〇c〇R5 group) are present. Further, the specific initiator is preferably a structure represented by the following formula (III).

In the formula (III), Ru-Rb means that each independently represents a hydrogen atom or a monovalent non-metal atomic group, and X represents a halogen atom (for example, a chlorine atom, a fluorine atom, an iodine atom or a bromine atom). Wherein at least two substituents selected from the group consisting of a C〇〇R2 group, a S03R3 group, a P〇3r4 group, a 〇H group, and a 〇c〇R5 group are present (wherein the 'R2, R3, R4, and rs systems are each independently A monovalent non-metal atom group is represented as Rl7 to R19 and X. The above formula is described in more detail below. In the general formula (I), R^R6 represents a aryl group or a heteroaryl group which may have a substituent, and examples thereof include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, and -16 - 200819915 xylyl group. , lysyl, fluorenyl, chlorophenyl, bromophenyl, chloromethylphenyl, phenyl, methoxyphenyl, ethoxyphenyl, phenoxyphenyl, phenyl acetate Benzyloxyphenyl, methylthiophenyl, phenylthiophenyl, methylaminophenyl, dimethylaminophenyl, ethylaminophenyl, carboxyphenyl, methoxythiobenzene , ethoxyphenyl group, phenoxy orthylphenyl, N-phenylaminoformamidophenyl, phenyl, cyanophenyl, sulfonylphenyl, sulfonylphenyl, A phosylphenyl group, a phosylphenyl group or the like. The heteroaryl group may be a group derived from a monocyclic or polycyclic aromatic ring containing at least one of nitrogen, oxygen and sulfur atoms. Specific examples of the heteroaryl ring of the heteroaryl group include, for example, thiophene, thiazide, furan, pyran, isobenzofuran, chromene, xanthene, morphine, pyrrole, pyrazole, Isothiazole, isoxazole, pyrimidine, pyrimidine, sorghum, tillage, isoindole, sulfhydryl, carbazole, anthracene, quinolin, isoquinoline, sorghum, naphthyridine, quinazoline, Porphyrin, 卩卩定, miso sitting, porphyrin, phenanthrene, η丫D定, perimidine, morphine, brewing, phenarsazine, morphine, φ Furoxan, etc., may further carry out benzene ring condensation, and may also have a substituent.

a substituent which the aryl or heteroaryl group of Ri~R6 may have, an alkyl group, an alkoxy group, a thioalkyl group or an aryl group having an amine group or an alkoxy group, a halogen atom, etc., an alkoxy group, a halogen The atom is better. The alkoxy group is particularly preferably a methoxy group or an ethoxy group, and preferably a halogen atom is fluorine or chlorine. The atomic group of one of R7 to R1G is preferably an alkyl group, and more preferably an alkyl group having 1 to 1 carbon atom, and examples thereof include a methyl group, an ethyl group, and a propyl group. From the viewpoint of hydrolysis, the carbon number is preferably small, preferably methyl or ethyl, and more preferably methyl. -17- 200819915 When the formula (π) ' R"~R16 represents a ~(iv) non-gold group, it preferably represents a substituted or unsubstituted alkyl, alkenyl or alkynyl group, a sulfanyl group, a sulfadienyl group. a group, a halogen atom, a substituted or unsubstituted aryl group thereof. Further, a preferred specific example of Rm to R16 will be described. Examples of the preferred alkyl group include a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. Hexyl, heptyl, octyl, decyl, decyl, undecyl, dodecyl, thirteen, hexadecyl, octadecyl, hexyl, isopropyl, isobutyl, second butyl , tert-butyl, isopentyl, neopentyl, 1-methylbutyl, isohexyl, 2-ethylhexyl, 2-methylhexyl, cyclohexyl, cyclopentyl, 2-norbornyl and the like. Among these, an alkyl group having a linear chain of 1 to 12 carbon atoms, a branched chain of 3 to 12 carbon atoms, and a cyclic alkyl group having 5 to 10 carbon atoms is more preferable. The substituent of the substituted alkyl group may be a group of a monovalent non-metal atomic group, and preferred examples thereof include a halogen atom (-F, -Br, -C1, -1), a hydroxyl group, an alkoxy group, an aryloxy group, Hydrogenthio, alkylthio, arylthio, alkyldithio, aryldithio, amine, N-alkylamino, hydrazine, hydrazine dialkylamino, N-arylamino, N,N- Diarylamine, N-alkyl-N-arylamino, decyloxy, aminomethyl methoxy, N-alkylaminomethyl methoxy, N-arylaminomethyl methoxy, N , N-二院基aminomethyl methoxy, N,N-diarylaminomethyl methoxy, N-homo-N-arylaminomethyl methoxy, alkyl sulfinium (alkyl Sulfoxy), aryl sulfoxy group, decyloxy group, acylthio group, amide group, N-alkyl guanylamino group, N-aryl decylamino group, ureido group, hydrazine '-Alkylureido, N', N'-dialkylureido, N,-arylureido, N,,N,-diarylureido, N,-alkyl-Ν'-arylureido, Ν- Alkyl urea, Ν-arylureido, hydrazine, -alkyl-hydrazine-alkylurea, Ν'-homo-anthracene-aryl-18- 200819915 Urea, N', N'-dialkyl-N- Alkylurea, N', N'-dialkyl-N-arylurea , Ν'-aryl-N-alkylureido, Ν'-aryl-N-arylureido, N',N'-diaryl-N-alkylureido, N',N'-diaryl --N-arylureido, Ν'-alkyl-Ν'-aryl-N-alkylureido, Ν'-alkyl-Ν'-aryl-oxime-arylureido, alkoxycarbenamine , aryloxycarbenyl, fluorene-homo-anthracene-homolyl carbamoyl, fluorene-homo-anthracene-aryloxycarbenyl, fluorene-aryl-hydrazine Carbocyclic amine, fluorene-aryl-hydrazine-aryloxycarbenyl, methionyl, fluorenyl, carbonyl, alkoxycarbonyl, aryloxycarbonyl, aminomethyl decyl, hydrazine-alkylamine Mercapto, fluorene, fluorenyl-dialkylaminomethyl fluorenyl, fluorenyl-arylaminomethyl fluorenyl, fluorene, fluorenyl-diarylaminomethyl fluorenyl, fluorenyl-alkyl-fluorene-aryl Aminomethyl sulfhydryl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, sulfonate (-so3h) and their conjugated bases (hereinafter referred to as sulfonate) Acid group), alkoxysulfonyl group, aryloxysulfonyl group, amine sulfinyl group, N-alkylamine sulfinyl group, N,N-dialkylamine sulfinyl group, N-aryl Amidoxime, N,N-diarylamine sulfinyl, N- Alkyl-N-arylamine sulfinyl, sulfonyl, N-alkylamine sulfonyl, N,N-dialkylamine sulfonyl, N-arylsulfonyl, anthracene, Ν·Diarylamine sulfonyl, N-alkyl-N-arylamine sulfonyl, phosphonic acid (-ΡΟ3 Η2) and its conjugated base (hereinafter referred to as phosphonate), dialkyl Phosphonic acid group (_Ρ〇3(alkyl) 2), diarylphosphonic acid group (-Ρ〇3(aryl) 2), alkylarylphosphonic acid group (-Ρ〇3(alkyl)(aryl) Base)), monoalkylphosphonic acid group (-Ρ 〇 3 Η (alkyl)) and its conjugated base (hereinafter referred to as alkylphosphonate), monoarylphosphonic acid group (-ΡΟ3Η (aryl) )) and its conjugated base (hereinafter referred to as arylphosphonate), phosphinomethoxy (-〇Ρ〇3Η2) and its conjugated base (hereinafter referred to as phosphonateoxy), dialkylphosphine醯oxy (-〇Ρ〇3(alkyl) 2), diarylphosphonium oxy (-〇Ρ〇3(aryl) 2), alkylarylphosphonium oxy (_0Ρ03 (alkane-19) - 200819915 yl)(aryl)), monoalkylphosphonium oxy (-〇Ρ〇3 Η(alkyl)) and conjugated base (hereinafter referred to as an anthracylphosphonicoxy group), an aryl group Phosphine Oxyl (-0Ρ03Η(aryl)) and a conjugated base (hereinafter referred to as an arylphosphonateoxy group), a cyano group, a nitro group, an aryl group, a heteroaryl group, an alkenyl group, an alkynyl group, and a decyl group. Specific examples of the alkyl group in the above substituents include the above alkyl group, and these may further have a substituent. Further, specific examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, a benzyl group, a decyl group, a chlorophenyl group, a bromophenyl group, a chloromethylphenyl group, and a hydroxyphenyl group. , methoxyphenyl, ethoxyphenyl, phenoxyphenyl, ethoxylated phenyl, benzamidine phenyl, methylthiophenyl, phenylthiophenyl, methylaminobenzene , dimethylaminophenyl, acetaminophen phenyl, carboxyphenyl, methoxycarbonylphenyl, ethoxyphenylcarbonyl, phenoxycarbonylphenyl, N-phenylaminocarbamyl Phenyl, phenyl, cyanophenyl, sulfonylphenyl, sulfonylphenyl, phosphonic phenyl, phosphonate phenyl, and the like. The heteroaryl group may be a group derived from a monocyclic or polycyclic aromatic ring containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom. Specific examples of the heteroaryl ring of the heteroaryl group include, for example, thiophene, thiazide, furan, pyran, isobenzofuran, chromene, xanthene, porphyrin, pyrrole, pyrazole, isothiazole. , isoxazole, pyrimide, pyrimidine, hydrazine trap, hydrazine trap, isoindole, sulfhydryl, carbazole, anthracene, quinolin, isoquinoline, hydrazine, naphthyridine, quinazoline, porphyrin , acridine, oxazole, porphyrin, phenanthrene, acridine, perimidine, morphine, sputum trap, morphine trap (?^1^"32111々), morphine 11 tillage, furosemide And the like, and the benzene ring may be further substituted, and may have a substituent. Further, the alkenyl group may, for example, be a vinyl group, a propylene group, a 1-butenyl group, a -20-200819915 cinnamyl group or a 2-chloro group. 1-vinyl group, etc. The alkynyl group may, for example, be an ethynyl group, a propynyl group, a 1-butynyl group, a trimethyldecyl ethynyl group, etc. Among the substituents of the substituted alkyl group, a more preferable one is preferable. There may be mentioned a halogen atom (-F, -Br, -Cl, -I), an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an N-alkylamino group, an N,N-dialkylamino group. , 醯oxy, N = alkylaminomethyl methoxy , N-arylaminomethyl methoxy, decyl, decyl, decyl, carboxy, alkoxycarbonyl, aryloxycarbonyl, aminomethyl fluorenyl, N-alkylaminocarbamyl , N,N-dialkylaminomethyl fluorenyl, N-arylaminomethyl fluorenyl, N-alkyl-N-arylaminomethyl fluorenyl, sulfonic acid, sulfonate, amine sulfonium , N-alkylamine sulfonyl, N,N-dialkylamine sulfonyl, N-arylamine sulfonyl, N-alkyl-N-arylamine sulfonyl, phosphonic acid, Phosphonate group, dialkylphosphonic acid group, diarylphosphonic acid group, monoalkylphosphonic acid group, alkylphosphonic acid group, monoarylphosphonic acid group, arylphosphonic acid group, phosphinomethoxy group, phosphine An acid group, an aryl group, an alkenyl group, an alkylene group (methylene group, etc.). On the other hand, the alkyl group of the substituted alkyl group may be, for example, removed from the above alkyl group having 1 to 20 carbon atoms. Any one of the hydrogen atoms and a divalent organic residue, preferably a linear one having a carbon number of 1 to 12, a branched carbon number of 3 to 12, and a carbon number of 5 to a cyclic alkyl group of 10; R μ~R 1 6 obtained by combining the above substituent with an alkyl group; Specific examples of the alkyl group include a chloromethyl group, a bromomethyl group, a 2-chloroethyl group, a trifluoromethyl group, a methoxymethyl group, a methoxyethoxyethyl group, an aryloxymethyl group, and a benzene group. Oxymethyl, methylthiomethyl, tolylthiomethyl, ethylaminoethyl, diethylaminopropyl, morpholinylpropyl, ethoxymethyloxy, benzhydryloxymethyl, Ν-cyclohexylaminomethyl methoxyethyl, Ν-phenylaminomethyl methoxy-ethyl-21- 200819915 base, acetamidoethyl, N-methylbenzimidyl propyl, 2 - side oxyethyl, 2-oxopropyl, carboxypropyl, methoxycarbonylethyl, aryloxycarbonylbutyl, chlorophenoxycarbonylmethyl, aminomethylmethylmethyl, N-A Aminomethylmercaptoethyl, N,N-dipropylaminomethylmethylmethyl, N-(methoxy:phenyl)aminocarbamidoethyl, N-methyl-N-( Sulfophenyl)aminomercaptomethyl, sulfonylbutyl, sulfonylpropyl, sulfonylbutyl, amine sulfinyl butyl, N-ethylamine sulfonylmethyl , N,N-dipropylaminesulfonylpropyl, N-triaminesulfonylpropyl, N-methyl-N-(phosphonophenyl)aminesulfonyloctyl, Acid butyl, phosphonic hexyl, diethylphosphonic butyl, diphenylphosphonic propyl, methylphosphonic butyl, methylphosphonic butyl, tolylphosphonic hexyl , tolylphosphonate hexyl, phosphinyloxypropyl, phosphonateoxybutyl, benzyl, phenethyl, α-methylbenzyl, methyl-1-phenylethyl, p-methylbenzyl, Cinnamyl, allyl, 1-propenylmethyl, 2-butenyl, 2-methylallyl, 2-methylpropenylmethyl, 2-propynyl, 2-butynyl, 3 - butynyl and the like. Preferred alkoxy groups of φ in Rn-Rb include a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms. The substituent which is present on the alkoxy group may be the same as the substituent on the above alkyl group. Further, specific examples thereof include a methoxy group and an ethoxy group, and a methoxy group is particularly preferred. Specific examples of the preferred aryl group of Rn to R16 include those in which one to three benzene rings form a fused ring, and a benzene ring and a 5-membered unsaturated ring form a fused ring. A phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a fluorenyl group, a fluorenyl group, and a fluorenyl group are mentioned, and among these, a phenyl group and a naphthyl group are more preferable.

Specific examples of the preferred substituted aryl group of Rn to Ri6 can be a substituent having a monovalent non-metal atomic group on the ring-forming carbon atom of the above-mentioned aryl-22-200819915 group. Examples of preferred substituents include the above-mentioned alkyl group and substituted group, and the substituted alkyl group as a substituent. Preferred examples of such a substituted aryl group include a biphenyl group, a tolyl group, a xylyl group, a decyl group, an yl group, a chlorophenyl group, a bromophenyl group, a fluorophenyl group, a chloromethylphenyl group, and the like. Fluoromethylphenyl, hydroxyphenyl, methoxyphenyl, methoxyethoxyphenyl, allyloxyphenyl, phenoxyphenyl, methylthiophenyl, tolylthiophenyl, Ethylaminophenyl, diethylaminophenyl, morpholinylphenyl, ethoxylated phenyl, benzamidine phenyl, N-cyclohexylaminomethyloxyphenyl, N-phenyl Aminomethyl methoxy phenyl, acetaminophen phenyl, N-methylbenzimidyl phenyl, carboxyphenyl, methoxycarbonylphenyl, aryloxycarbonylphenyl, chlorophenoxy Carbonylphenyl, aminomethylphenylphenyl, N-methylaminoformamidophenyl, N,N-dipropylaminocarbamiphenyl, N-(methoxyphenyl)amine Methyl phenyl, N-methyl (sulfonyl phenyl) aminomethyl decyl phenyl, sulfonyl phenyl, sulfonyl phenyl, sulfonyl phenyl, N-ethyl sulfonate Nonylphenyl, N,N-dipropylaminesulfonylphenyl, N-methylphenylsulfonylphenyl, N-A (phosphonophenyl)amine sulfonylphenyl, phosphonic phenyl, phosphonate phenyl, diethylphosphonic phenyl, diphenylphosphonic phenyl, methylphosphonic acid Phenyl, methylphosphonate phenyl, tolylphosphonic phenyl, tolyl phenyl phenyl, allyl phenyl, 1-propenylmethylphenyl, 2-butene basic, A Allyl phenyl, 2-methylpropenyl phenyl, 2-propynyl phenyl, butynyl phenyl, 3-butynyl phenyl, and the like. Further, preferred examples of R12 include a halogen atom, and a preferred example is an ortho substitution. More preferably, a chlorine atom is mentioned. The specific initiator having the structure of -23-200819915 is known to have a structurally large electron accepting area by a steric hindrance of a chlorine atom, and has a particularly high sensitivity. This high sensitivity effect is particularly remarkable when a chlorine atom is substituted in the ortho position of the aryl group, and is an important condition for selecting a compound. In the present invention, a specific initiator having a hydrophilic group on its skeleton can maintain a dissolved state which does not precipitate in the developing solution. The hydrophilic group is a hydroxyl group, a hydroxycarbonate group, a carboxylate, a sulfonate group or a phosphate group, and a hydroxyl group is more preferably used in a weakly acidic aqueous solution, and a hydroxycarbonate group or a carboxylate group is used in an aqueous alkali solution. Better. Although the hydroxyl group is sufficiently soluble in the aqueous alkali solution, the water resistance of the lithographic printing plate tends to be somewhat lowered because of its hydrophilicity. Therefore, it can be said that it is more preferable than the hydroxyl group in the base system, the perfluorocarbon group which is itself protected by the hydrolyzable group, and the carboxylic acid ester which is water-soluble by hydrolysis. When the hydrophilic group is used, in the method for producing a lithographic printing plate of the present invention, even if a large amount of the photosensitive layer component is dissolved in the developing liquid, no Φ initiator component is precipitated from the developing liquid, and the developing machine is contaminated or It is a situation in which a developing gas is generated and the layout is deteriorated. In other words, it is very useful to control the maintenance load of the machine to a minimum, which can reduce the cost and improve the workability. Hereinafter, preferred examples of the diimidazole-type compound of the present invention (exemplified compound 1-1 to exemplified compound 1-24) are shown, but are not limited thereto.

-24- 200819915

CKo mV

1-5 Ρ〇2Μβ

:»Q COjMe COjM© t/yiLn n^-jLn -rk, puO" Μβ〇2〇 Me〇sC 1-6 1-7 1-8

A method for synthesizing the compound represented by the formula (I) will be described. [Synthesis of exemplified compound (1-1)] After mixing 3.7 g of potassium hexacyanoferrate, 3.1 g of potassium hydroxide, 70 ml of water and 40 ml of toluene, the mixture was stirred at room temperature until the solid disappeared. - Subsequently, 3.8 g of the following compound (Γ-1) was added, the oil bath was heated to 80 ° C, and stirred under reflux for 4 hours. After the reaction liquid which was stirred under reflux for 4 hours was allowed to cool, 100 ml of water was added and extracted with toluene to obtain an organic layer formed in toluene, -25-200819915, using an aqueous solution of sodium chloride, followed by washing with water. After washing, the organic phase was concentrated to give a red oil. The obtained liquid was recrystallized using methanol to obtain 2·9 g of the objective compound (I-1).

Other diimidazole-type compounds can also be synthesized in the same manner by appropriately selecting a starting material, a compound to be added, and the like. The diimidazole-type compound of the photosensitive composition of the present invention is preferably contained in an amount of from 0.5 to 20% by mass, more preferably from 1 to 10% by mass, based on the total solid content of the photosensitive composition. In the present invention, in addition to the specific diimidazole type compound described above, other well-known photopolymerization initiators, thermal polymerization initiators and the like may be selected without damaging the effects of the present invention. Examples of the polymerization initiator which can be used include, for example, a well-known sulfonium salt having a decanoic acid structure in a bication portion, a tri-trap compound having a trihalomethyl group, a peroxide, and an azo polymerization. Initiator, azide compound, quinonediazide, and the like. Specific examples of the iron salt of a preferred polymerization initiator which can be used include those described in paragraphs [003 0] to [0 0 3 3 ] of JP-A-200 1 _ 1 3 3 969. When another polymerization initiator is used, the content is preferably 50% by mass or less based on the specific diimidazole type compound. The radical generating agent (the specific diim- 26-200819915 azole type compound and the initiator used as necessary) which can be used in the present invention preferably has a maximum absorption wavelength of 500 nm or less, and 400 nm. The following is better. (B) Sensitized colorant The sensitizing coloring matter used in the photosensitive composition of the present invention preferably has an absorption peak (maximum absorption wavelength) at 305 to 850 nm. Such a sensitizing coloring material may be a dye or a pigment shown below which is a photosensitive coloring material and a light absorbing light source and interacting with a photopolymerization initiator. Preferred photosensitive photosensens or dyes include polynuclear aromatics (for example, anthraquinone, anthracene, tri-ortylene), xanthene (for example, luciferin, eosin, erythromycin, rhodamine B). , rose red), anthocyanins (such as thiablycine, anthocyanin), merocyanines (such as merocyanine, carbon, cyanine), tiofia (for example, thiazide, sub Blue, toluidine blue), acridine (eg, acridine orange, chloroflavon, acridine yellow), indigo (eg, indigo, metal indigo), porphyrins (eg, tetraphenyl) Porphyrins, central metal-substituted porphyrins, chlorophylls (eg, chlorophyll, chlorophyllin, central metal-substituted chlorophyll), metal complexes, terpenoids (eg, onion), horn shark keys (eg, snail key) )Wait. For example, the styrene dyes described in JP-A-37-13034, and the cationic dyes described in JP-A-62-143044, and JP-A-59-234噚 特 特 特 特 蒽醌 蒽醌 蒽醌 蒽醌 蒽醌 蒽醌 蒽醌 蒽醌 蒽醌 蒽醌 蒽醌 蒽醌 蒽醌 蒽醌 蒽醌 蒽醌 蒽醌 蒽醌 蒽醌 蒽醌 蒽醌 蒽醌 蒽醌 蒽醌 蒽醌 蒽醌 蒽醌 蒽醌 蒽醌 蒽醌 蒽醌 蒽醌 蒽醌 蒽醌 蒽醌 蒽醌 蒽醌 蒽醌 蒽醌 蒽醌 蒽醌 蒽醌 蒽醌 蒽醌 蒽醌 蒽醌 特Benzene xanthene dyes, which are described in the Unexamined-Japanese Patent Publication No. Hei. No. Hei. No. Hei. In the case of the pyridinium salt, the sulphuric acid coloring matter described in the publication of the Japanese Patent Publication No. Sho 46-423 No. -27-200819915 The conjugated ketone coloring matter disclosed in each of the publications of Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. Anthocyanin derivative described in Japanese Unexamined Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. In the bulletin, JP-A-6- 3 1 8 4 8 and JP-A-62-1-443, each of the bullets, and the public body of the public, No. 5 9 - 2 8 3 2 5 The amino acid described in the publication of the Japanese Patent Publication No. JP-A No. 61-96, and the color material described in Japanese Patent Publication No. Hei. A part of the cyanine color material described in the Unexamined-Japanese-Patent No. 2-244050, and the part of the cyanine color material described in the Japanese Patent Publication No. Sho 59-89303 The phthalocyanine coloring material described in the publication No. 129257, and the benzopyran coloring material described in JP-A-8-3839897. Further, in particular, the following infrared absorbing agents (dyes or pigments) can also be suitably used as the sensitizing colorant. The anthocyanins described in, for example, Japanese Laid-Open Patent Publication No. Hei 59- No. Hei. Dye, anthocyanin dyes and the like described in the specification of British Patent No. 4 3 4,87.5. Further, the infrared absorbing sensitizer described in the specification of U.S. Patent No. 5,155,93,8 is also applicable, and the substituted arylbenzene described in the specification of U.S. Patent No. 3,8 8 1,9 2 4 And the three-methylthiopyridine salt of -28-200819915, which is described in the specification of U.S. Patent No. 4,327,169, which is described in the specification of U.S. Patent No. 4,327,169, and the Japanese Patent Publication No. 5-8-108 1 0 5 No. 1, No. 5, No. 8-220, No. 1, No. 59-41363, No. 59-84248, No. 59-84249, No. 5 9- 1 46 063, and No. 5 9- 1 4606 The pyridyl key compound, the anthocyanin color material described in JP-A-59-2 1 6 1 46, the pentamethylthiopyridine salt described in the specification of U.S. Patent No. 4,283,475, or the like. The pyridyl compound described in the publication No. -13514 and the publication No. 5-197702 can also be suitably used. Further, preferred dyes include the infrared absorbing dyes described in the formulas (I) and (II) of the specification of U.S. Patent No. 4,756,993, and the indigo dyes described in the specification of European Patent No. 9 165 1 3 A2. Further, the anionic infrared absorbing agent described in the specification of Japanese Patent Application No. Hei No. 0-799 No. 1 is also suitable for the ruthenium. Here, the anionic infrared absorbing agent means a substance having an anionic structure in which a mother nucleus which substantially absorbs infrared rays has no cationic structure. For example, (b 1) an anionic metal complex, (b 2) an anionic carbon black, (b3) an anionic indigo, and (b4) a compound represented by the following formula A may be mentioned. The dianion of these anionic infrared absorbing agents contains a monovalent cation of a proton or a polyvalent cation. Formula A [Ga·-M-Gb]m Xm + Here, (b 1) an anionic metal complex refers to a central metal which substantially absorbs light in a complex portion and an anion in the entire ligand. Things. (b2) The anionic carbon black may be a carbon black in which an anion group such as a sulfonic acid, a carboxylic acid or a phosphonic acid group is bonded as a substituent. The introduction of these groups into carbon black can be specified by the third edition of Carbon Black Handbook (edited by the Carbon Black Association, issued on April 5, 995, issued by the Society of Carbon Black-29-200819915). Acid means to oxidize carbon black. (b3) Anionic indigo refers to an anion group exemplified in the above description of (b2) bonded to the indigo skeleton, and the whole is an anion. Next, the compound represented by the above formula (b4) Formula A will be described in detail. In the above formula A, Ga· represents an anionic substituent, and Gb represents a neutral substituent. Xm + represents a cation having a valence of 1 to m of a proton, and m 0 represents an integer of 1 to 6. The lanthanide represents a conjugated bond, and the conjugated ruthenium may have a substituent or a ring structure. The conjugated bond Μ can be expressed by the following formula: ^(C(^Kl) = C(-R2))n^C^(^R3) = In the above formula, R^R2, ! ^ each independently represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a carbonyl group, a thio group, a sulfonyl group, a sulfinyl group, an oxy group, an amine group, and the like. They can be joined to each other to form a ring structure. The η system represents an integer of 1 to 8. Further, a cationic infrared ray absorbing agent or a nonionic infrared absorbing agent φ can also be suitably used. For other dyes, commercially available dyes and those known in the literature such as "Dyestuffs" (edited by the Organic Synthetic Chemistry Association, Showa 45) are well known. Specific examples thereof include an azo dye, a metal salt azo dye, a pyrazolone azo dye, a naphthoquinone dye, an anthraquinone dye, an indigo dye, a carbon dye, a quinone imine dye, and a methine dye. , dyes such as dihroscopic dyes, amine iron dyes, shark key pigments, metal thiolate complexes, and the like. In addition, it is possible to use a pigment which is a sensitizing coloring material, and it is possible to use a commercially available pigment and color number (C · I ·), a "newest pigments" (Japanese pigment technology 30 · 200819915 association, 1 977), Pigments described in "The Latest Pigment Application Technology" (CMC Publishing, 1986), "Printing Ink Technology" (CMC Publishing, 1 984). For example, examples of the type of the pigment include a black pigment, a yellow pigment, a dial pigment, a brown pigment, a red pigment, a violet pigment, a blue pigment, a green pigment, a fluorescent pigment, a metallic powder pigment, and a polymer-bonded colorant. Specifically, an insoluble azo pigment, an azo magenta pigment, a condensed azodicarb, a azo pigment, an indigo pigment, an anthraquinone pigment, an anthracene and a violet φ cyclic ketone pigment, a thioindigo pigment, and a quinine can be used. Anthrone-based pigments, diterpene trap pigments, isoindolinone pigments, quinoline yellow pigments, dyed lake pigments, sputum pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, Inorganic pigments, carbon black, etc. Among these pigments, carbon black is preferred. These pigments may be used without surface treatment or may be applied by surface treatment. The surface treatment method may consider a method of coating a resin or a wax on the surface; a method of adhering the surfactant; and bonding a reactive substance (for example, a decane coupling agent, an epoxy compound, a polyisocyanate, etc.) to the surface of the pigment. Method, etc. The above surface treatment methods are described in "The Properties and Applications of Metallic Sodium" (Lucky House), "Printing Ink Technology" (CMC Publishing, 1984) and "Latest Pigment Application Technology" (CMC Publishing, 1 986 issue). The particle diameter of the pigment is preferably from 0.01 μm to 10 μm, more preferably from 0.05 μm to 1 μm, particularly preferably from 0.1 μm to 1 μm. The method of dispersing the pigment can use a well-known technique used in the production of inks and toners. The dispersing machine can be exemplified by ultrasonic disperser, sand mill, vertical ball mill, particle mill, super speed honing machine, ball mill, -31- 200819915 blade turbine, disperser, KD mill, colloid mill, negative resistance Pipe machine, three-roll mill, pressure kneader, etc. The "Latest Pigment Application Technology" (CMC Publishing, 1986) is described in detail. More preferred examples of the sensitizing coloring material of the present invention include those described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. 6-1-96. The part of the cyanine color material, the part of the cyanine color material described in the Unexamined-Japanese-Patent No. 2 - 2 4 4 0 0 0, and the part of the flower cyan φ material described in the Gaza 59-2 8 3 26 In the section of the squid, the squid, and the shoji, the shoji, the shoji, the shoji, the shoji, the shoji, the shoji, the shoji, the sho. Benzopyran coloring material. And the infrared absorbing agent described in JP-A-U-209001. The sensitizing colorant of the present invention is preferably used alone or in combination of two or more. Further, the photopolymerizable composition of the present invention may be added as a co-sensitizer with a compound known to have an effect of improving sensitivity or inhibiting polymerization by oxygen. • The structure in which these sensitizing pigments are used, whether they are used alone or in combination, and how to use them, can be appropriately set in accordance with the performance design of the final material. For example, by using two or more kinds of sensitizing pigments, the compatibility with the photosensitive composition layer can be improved. When the sensitizing colorant is selected, in addition to the photosensitivity, the Mohr absorption coefficient at the light-emitting wavelength of the light source is an important factor. Since the coloring material can be used in a large amount by using a molar absorption coefficient, since the amount of the coloring material can be relatively small, it is economical, and when used in a lithographic printing plate precursor, it is advantageous from the film properties of the photosensitive layer. . Since the sensitivity of the photosensitive layer, the resolution, or the physical properties of the exposed film are greatly affected by the absorbance at the wavelength of the light source, it is preferable to appropriately set the addition amount of the sensitized colorant. In the lithographic printing plate used for a relatively thin film thickness, the amount of the sensitizing colorant added in the photosensitive layer is set to be in the range of 0.25 to 1 in the range of 0.25 to 1 in which the absorbance of the photosensitive layer is 0.1 to 1.5. When it is used as a lithographic printing plate, the amount of the sensitizing colorant is usually 0.05 to 30 parts by mass, preferably 0.1 to 20 parts by mass, and preferably 0.2 to 10 parts by mass, based on 100 parts by mass of the photosensitive layer component. The range of parts is better. When the sensitizing colorant of the present invention is used as a lithographic printing plate precursor, various chemical modifications can be carried out in order to improve the characteristics of the photosensitive layer. For example, by bonding a sensitizing colorant to an addition polymer compound structure (for example, an acrylonitrile group or a methacrylic acid group) by a covalent bond, an ionic bond, a hydrogen bond, or the like, the exposed film can be made high in strength. Or performing unnecessary precipitation of the colorant from the film after the exposure is suppressed. Further, when the photosensitive composition of the present invention is used as a master for a lithographic printing plate, a hydrophilic portion (carboxyl group and ester thereof) is introduced in order to improve the handling suitability of the photosensitive layer for a preferred (alkali) aqueous developing solution. An acid group or a polar group such as a sulfonic acid group or an ester thereof or an oxiranyl group is effective. In particular, the hydrophilic group of the ester type is characterized in that it has a relatively hydrophobic structure and is excellent in compatibility in the photosensitive layer, and the hydrophilicity is increased by the hydrolysis to form an acid group in the developing solution. Further, for example, in order to improve the compatibility in the photosensitive layer and suppress crystallization, an appropriate substituent can be introduced. For example, in order to extract the square base or the compatibility of unsaturated bonds such as propyl groups, a certain photosensitive system is very effective, and by introducing a branched alkyl-33-200819915 structure or the like, By introducing a steric barrier between the π planes of the coloring matter, crystallization can be remarkably suppressed. Further, by introducing a phosphonic acid group, an epoxy group, a trialkoxy sand compound, or the like, adhesion to an inorganic substance such as a metal or a metal oxide can be improved. Further, it is also possible to use a method such as polymerization according to the purpose. In the above sensitizing coloring matter, a sensitizing coloring agent capable of forming a high sensitivity initiating line with a bismuth-type compound having a structure represented by the above formula (I), which is selected from a coumarin coloring material and a styrene coloring material It is better to use an anthocyanin coloring agent or a sage coloring material. These sensitizing pigments are used in such a structure, used alone or in combination of two or more, and the amount of addition, and can be appropriately set in accordance with the performance of the final material. For example, by using two or more kinds of sensitizing pigments, the compatibility with the photosensitive composition layer can be improved. When the sensitizing colorant is selected, in addition to the photosensitivity, the Mohr absorption coefficient at the light-emitting wavelength of the light source is an important factor. Because by using the More absorption coefficient large color material, since the additive amount φ of the color material becomes relatively small, it is economical, and when used in the lithographic printing plate precursor, the film properties of the photosensitive layer are also compared. advantageous. Since the photosensitivity of the photosensitive layer, the resolution, or the physical properties of the exposed film are greatly affected by the absorbance at the wavelength of the light source, it is preferable to appropriately set the amount of addition of the sensitized toner. Among them, for the purpose of hardening a thick film of 5 μm or more, there is a case where the low absorbance is low and the degree of hardening can be improved. In the lithographic printing plate used for a relatively thin film thickness, the amount of the sensitizing colorant added during use is set in the range of 0. 1 to 1.5 in the photosensitive layer, preferably in the range of 0.25 to 1. . When it is used as a lithographic printing plate, the amount of the sensitizing colorant is usually 0.05 to 30 parts by mass, preferably 0 to 1 part by mass to 0 parts by mass, based on 100 parts by mass of the photosensitive layer component -34 to 200819915. 〇· 2~1 〇 The range of parts by mass is better. (C) Polymer compound The polymerizable compound used in the photosensitive layer of the present invention is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and is selected from compounds having at least one, preferably two or more compounds. Usually, it is a compound capable of generating an addition polymerization reaction by at least one of a radical or an acid. Such a group of compounds is widely known in the industrial field, and the present invention can be used without limitation. These have chemical forms such as monomers, prepolymers, i.e., dimers, trimers, and oligomers, or copolymers of these, and mixtures thereof. As an example of the monomer, an unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), or an ester thereof or a guanamine can be used, preferably. It is an ester of an unsaturated carboxylic acid and an aliphatic polyol compound, and an amide of an unsaturated carboxylic acid and an aliphatic polyamine compound. Further, an unsaturated carboxylic acid ester having a nucleophilic substituent such as a hydroxyl group, an amine group or a thiol group, or an addition reaction product of a monofunctional or polyfunctional isocyanate or epoxy group, and a monofunctional or A dehydration condensation reaction product of a polyfunctional carboxylic acid or the like can also be suitably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or an oxime amine having an isocyanate group or an electrophilic substituent such as an epoxy group, and a monofunctional or polyfunctional alcohol, an amine or a thiol, The unsaturated carboxylic acid ester having a halogen-based or p-toluenesulfonyloxy group-releasing substituent or a substituted reactant of a guanamine and a monofunctional or polyfunctional alcohol, an amine or a thiol is also suitable. Further, as another example, a group of compounds obtained by substituting the above unsaturated carboxylic acid with an unsaturated phosphonic acid, styrene, ethyl-35-200819915 alkenyl ether or the like can also be used. Specific examples of the monomer of the aliphatic polyol compound and the ester of the unsaturated carboxylic acid, such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, butylene glycol Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, tricarboxymethyl triacrylate, dicarboxymethyl propyl tris(propylene oxypropyl) ether, triterpene methyl ketone triacrylate Ester, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, neopentyl alcohol diacrylate, neopentyl alcohol triacrylate, neopentyl alcohol tetraacrylate Ester, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, ginseng Acryloxyethyl)trimeric isocyanate, trimeric isocyanate E oxime modified triacrylate, polyester acrylate oligomer, and the like. Methacrylates are tetraethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane Trimethacrylate, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, neopentyl Alcohol trimethacrylate, neopentyl alcohol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbose Alcohol tetramethacrylate, bis[p-(3-methylpropenyloxy-2-hydroxypropoxy)benzene]methylmethane, bis-[p-(methacryloxyethoxyethoxy) Phenyl] dimethylmethane and the like. Ikonic acid esters are ethylene glycol dicone ester, propylene glycol diconcanate, -36- 200819915 1,3-butanediol diconconate, 1,4-butanediol diconconate , tetraethylene glycol diconconate, neopentyl alcohol diconconate, sorbitol tetraconcanate, and the like. The crotonate is ethylene glycol dicrotonate, tetraethylene glycol dicrotonate, neopentyl dicrotonate, sorbitol tetracrotonate, and the like. The isocrotonate includes ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, sorbitol tetraisocrotonate, and the like. Maleic acid esters include ethylene glycol di-n-butyl succinate, triethylene glycol di maleate, neopentyl alcohol di maleate, sorbitol tetramaleic acid Ester and the like. Examples of the other esters include, for example, the aliphatic alcohol esters described in Japanese Patent Publication No. 5 1 - 4 7 3 3 4, and JP-A-59-196236, or JP-A-5-9-5240 5 9-524 1. The product having an aromatic skeleton described in JP-A No. 2-2261-4, and the amine group-containing product described in JP-A No. 1 -1 6 5 6 1 3 . Further, the aforementioned ester monomers can also be used in the form of a mixture. Further, specific examples of the monomer of the aliphatic polyamine compound and the decylamine of the unsaturated carboxylic acid are methylene bis acrylamide, methylene bis methacrylamide, 1,6-hexamethylene bis propylene. Indoleamine, 1,6-hexamethylenebismethacrylamide, diethylenetriaminetripropenylamine, benzodimethylbisacrylamide, benzodimethyldimethacrylate, and the like. Other preferred guanamine-based monomers include those having a cyclohexene structure as described in JP-A-54-2 1726. In addition, a urethane-based addition polymerizable compound prepared by an addition reaction of an isocyanate and a hydroxyl group is also preferable, and a specific example thereof is described in JP-A-48-41708. a polyisocyanate compound having two or more isocyanate groups, and a vinyl group containing a hydroxyl group represented by the following formula (A), which has two or more polymerizations in one molecule - 37-200819915 vinyl group A vinyl urethane compound or the like. CH2 = C(R4)COOCH2CH(R5)OH (a) (wherein, in the formula (a), R4 and R5 are Η or CH3), and the special opening 5b, 37,193, special fair, 2-32293, And the urethane urethanes described in JP-A-February 2, No. 6,765, No. 5, No. 8 8-498, No. 5, No. 5, No. 5, No. 5, 654, No. A urethane compound having an ethylene oxide skeleton as described in No. 39418 is also preferred. Further, an addition having an amine structure or a sulfide structure in the molecule described in JP-A-63-27765, JP-A-63-260909, and JP-A-1-10538 As the polymerizable compound, a photopolymerizable composition having a very excellent photospeed can be obtained. Other examples include polyester acrylates and rings described in each of the publications of Japanese Patent Publication No. Sho 4-8-64, No. 4, No. 4, No. 4, No. A multifunctional acrylate or methacrylate such as an epoxy resin or an epoxy acrylate such as (meth)acrylic acid. Further, for example, a specific unsaturated compound described in each of the publications of Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The vinyl sulfonic acid compound described. Further, in some cases, the perfluoroalkyl group-containing structure described in JP-A-61-22048 is suitably used. Further, it is also possible to introduce a photocurable monomer and an oligomer by using the Japanese Adhesive Society Publication No. 20, No. 7, and No. 3 00 to 308 (1 984). The structure of the addition polymerizable compound, the use alone or in an amount, and the method of using the additive amount can be arbitrarily set in accordance with the final performance design of the curable composition -38·200819915. For example, it can be selected from the following points of view. From the viewpoint of sensitivity, a structure having a large content of unsaturated groups per molecule is preferred, and most of the cases are preferably a bifunctional group or more. Further, in order to increase the strength of the cured film, it is more preferable to use a trifunctional or higher functional group, and further, different functional groups and different polymerizable groups (for example, acrylate, methacrylate, styrene compound, vinyl) The ether compound) is also effective in adjusting the sensitivity and the strength of both sides. Moreover, the compatibility and dispersibility of other components (for example, a binder polymer, a polymerization initiator, a coloring agent, etc.) in a photosensitive layer, and the selection and use of a polymeric compound are important factors, for example by using Two or more kinds of low-purity compounds or hydrazines can improve compatibility. Further, in order to improve adhesion to a substrate or the like, a specific structure can be selected. The above polymerizable compound is preferably used in the range of 5 to 80% by mass, more preferably in the range of 25 to 75% by mass, based on the total solid content of the photosensitive layer. Further, these may be used alone or in combination of two or more. Further, the method of using the polymerizable compound can arbitrarily select an appropriate structure, blending, and addition amount from the viewpoints of inhibition of oxygen polymerization, size, resolution, whitening property, refractive index change, surface adhesion, and the like. According to the situation, the undercoating, the top layer structure and the coating method are considered. <(D) Binder Polymer> When the photosensitive composition of the present invention is applied to the photosensitive layer of the original plate for a lithographic printing plate of the preferred embodiment, the photopolymerization initiating system and the addition polymerizable compound are not mentioned above. In addition, it is preferred to use a binder polymer. The binder polymer contained in the photosensitive composition of the present invention has a function as a film forming agent of a light-sensitive agent of 39-200819915, and preferably contains a linear organic polymer. Any of these "linear organic high molecular polymers" can be used. Examples of such a binder polymer are selected from the group consisting of acrylic resins, polyvinyl acetal resins, polyurethanes, polyamide resins, epoxy resins, methacrylic resins, styrene resins, and poly The polymer of the ester resin is preferred. Among them, an acrylic resin or a polyurethane resin is preferred. Further, in order to increase the film strength of the image portion, the binder polymer may have crosslinkability. In order to impart crosslinkability to the binder polymer, a crosslinkable functional group such as an ethylenically unsaturated bond may be introduced into the main chain of the polymer or into the side chain. Crosslinking agent The functional group can be introduced by copolymerization or by a polymer reaction. Here, the crosslinkable group means a process of causing a radical polymerization reaction in the photosensitive layer when the lithographic printing plate precursor is exposed, and a polymer binder can be crosslinked. In the case of such a group, the functional group capable of undergoing the addition polymerization reaction may, for example, be an ethylenically unsaturated bond group, an amine group or an epoxy group. Further, a functional group of a radical may be obtained by light irradiation, and examples of such a crosslinkable group include a thiol group, a halogen group, and a key salt structure. Among them, an ethylenically unsaturated bond group is preferred, and a functional group represented by the following general formulae (1) to (3) is particularly preferred. In the above formula (1), :1 to R3 each independently represent a hydrogen atom or a monovalent organic group, and R1 may be a hydrogen atom or an alkyl group which may have a substituent is -40-200819915 Since the hydrogen atom and the methyl group have high radical reactivity, it is preferred. Further, R2 and R3 each independently represent a hydrogen atom, a halogen atom, an amine group, a carboxyl group, an alkoxycarbonyl group, a sulfonic acid group, a nitro group, a cyano group, an alkyl group which may have a substituent, and an aromatic group which may have a substituent. Alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylamino group which may have a substituent, an arylamine group which may have a substituent, an alkylsulfonyl group which may have a substituent, The arylsulfonyl group having a substituent, wherein the radical has high reactivity, it is preferably a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, a substituent group which may have a substituent, and an aryl group which may have a substituent. X represents an oxygen atom, a sulfur atom or N(R12)·, and R12 represents a hydrogen atom or a monovalent organic group. Here, R12 may, for example, be an alkyl group which may have a substituent. Among them, a hydrogen atom, a methyl group, an ethyl group or an isopropyl group is preferred because of high radical reactivity. Here, examples of the substituent which 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 amine group, an alkylamino group, an arylamine group, a residue, and a substituent. Oxyl group, acid extension group, nitro group, amino group, aramidyl group, alkylsulfonyl group, arylsulfonyl group and the like. Ff R5 B6 R7 General formula (2) In the above formula (2), R4 to R8 each independently represent a hydrogen atom or a monovalent organic group, and R4 to R8 include a hydrogen atom, a halogen atom, an amine group, and the like. An alkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfonic acid group, a nitro group, a cyano group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an anthracene group which may have a substituent, may have a substituent An aryloxy group, an alkylamino group which may have a substituent, an arylamine group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, wherein Further, a hydrogen atom, a carboxyl group, an alkoxy ore group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are preferred. The substituent which can be introduced can be exemplified by the same formula as (1). Further, Y represents an oxygen atom, a sulfur atom, or N(Ri2). The Ri2 system is synonymous with the case of R12 of the general formula (1), and preferred examples are also the same. —z-o^? General (3)

R9r10 In the above formula (3), R9 is preferably a hydrogen atom or a substituent group which may have a substituent, and among them, a hydrogen atom or a methyl group is preferred because of high radical reactivity. R^'R11 each independently includes a hydrogen atom, a halogen atom, an amine group, a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfonic acid group, a nitro group, a cyano group, an alkyl group which may have a substituted fluorene group, and An aryl group having 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 arylamine group which may have a substituent, and a fluorenyl group which may have a substituent a sulfonyl group, an arylsulfonyl group which may have a substituent, wherein, since the radical reactivity is relatively preferable, a hydrogen atom, a fluorenyl group, an aristocratic iron group, an alkyl group which may have a substituent, may have a substituent The aryl group is preferred. Here, the substituent which can be introduced can be exemplified by the same formula (1). Further, Z represents an oxygen atom, a sulfur atom, or -N(R13)-, or a phenyl group which may have a substituent. R13 may, for example, be a hospital base or the like which may have a substituent. Among them, a methyl group, an ethyl group and an isopropyl group are preferred because of high radical reactivity. Among the above, a (meth)acrylic acid copolymer and a polyurethane having a crosslinkable group in a side chain are more preferable. -42· 200819915 A crosslinkable binder polymer such as a radical (a polymerization-initiating radical or a growth radical of a polymerizable compound in a polymerization process) is added to its crosslinkable functional group, directly between the polymers Alternatively, the addition polymerization is carried out through a polymerization chain of a polymerizable compound, and crosslinking is formed between the polymer molecules to be hardened. Or, an atom in the polymer (for example, a hydrogen atom on a carbon atom adjacent to the crosslinking group) is extracted by a radical to form a polymer radical, which forms a crosslink between the polymer molecules by bonding each other. And hardened. The content of the crosslinkable group in the binder polymer (the content of the unsaturated double bond capable of radical polymerization by iodine titration), 〇·1~1 〇·〇 mmol per 1 gram of the binder polymer The ear is better, preferably 1 _0 to 7.0 millimolar, and most preferably 2.0 to 5.5 millimolar. Further, in the plate making step of the lithographic printing plate precursor, in order to remove the non-image portion of the photosensitive layer well, the binder polymer to be used can be appropriately selected in accordance with the state of development processing. The details are described below. (D-1) The alkali-soluble binder polymer is used in the development process using an alkali imaging solution because the binder polymer must be dissolved in the alkali imaging solution to be used in the water test device to be soluble or moist. A bulging organic high molecular polymer is preferred. In particular, when an alkali developing solution having a pH of 1 Torr or more is used, an alkali-soluble binder is preferably used. In order to have solubility in alkaline water, it is preferred to have an alkali-soluble group. The alkali-soluble group may, for example, be a carboxyl group, a phenolic hydroxyl group, a sulfonylamino group, an imine group, a sulfonic acid group or a phosphoric acid group. The alkali-soluble group in the polymer is preferably me.2 meq/g or more and 6.0 meq/g or less from the viewpoint of alkali solubility and printing durability. It is more preferably 0.5 meq/g or more and 4.0 meq/g or less, and more preferably l.Orneq/g or more -43 to 200819915 3.5 meq/g or less. Hereinafter, the alkali-soluble group will be described in detail. The method of introducing a carboxyl group into a binder polymer can be carried out by half-esterifying an anhydride having an unsaturated double bond such as methacrylic acid, acrylic acid, itaconic acid, crotonic acid, maleic acid or fumaric acid. a monomer, a monomer obtained by semi-aminating an anhydride having an unsaturated double bond, a carboxyphenylmethacryl oxime, a carboxyphenyl propylene oxime, a carboxy styrene, a 2-carboxyethyl acrylate, a The 2-carboxyethyl acrylate and the general formula (b) described in JP-A-2000-3 3265 are obtained by polymerization. In the formula (b), R1 and R2 represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a carboxyl group, or the like. R3 represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group. X is a divalent linking group, and, for example, an alkylene group or a phenyl group which may have a substituent may be suitably used. The Y-based aromatic group having a substituent may be, for example, a stretching phenyl group or a stretching naphthyl group which may have a substituent. The method of introducing a phenolic hydroxyl group can be carried out by using hydroxyphenylmethacrylamide, hydroxyphenyl acrylamide, hydroxystyrene, hydroxyphenyl maleimide, JP-A-2000-3 30265 The monomer of the above formula (a) is obtained by copolymerization. In the formula (a), R1 and R2 represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a carboxyl group, and the like. R3 represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group. X is a divalent linking group, and examples thereof include an alkyl group which may have a substituent or a phenyl group. Y is a divalent aromatic group which may have a substituent, and may, for example, be a phenyl group or a naphthyl group which may have a substituent. The method of introducing a sulfonamide group is exemplified by the monomer of the formula (C) described in JP-A-200-200819915, and the disclosure of JP-A-H09-18914. Specific examples of the monomer of the formulae (I) to (v) include m-amino-m-sulfonyl phenyl methacrylate, N-(p-aminosulfonylphenyl)methacrylamide, and N- (Aminosulfonylphenyl) acrylamide and the like. In the formula (c)', R1 and R2 represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a carboxyl group, or the like. R3 represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group. The x-form represents a divalent linking group, and may, for example, be an alkylene group or an extended aryl group which may have a substituent. The Y group represents a divalent aromatic group which may have a substituent, and may, for example, be a phenyl or anthracene group which may have a substituent. The method of introducing an imine group can be obtained by copolymerizing N-(p-toluenesulfonyl)methacrylamide, N-(p-toluenesulfonyl)propeneamine or the like. The sulfonic acid group can be made by having styrenesulfonic acid and its salt, 2-propenylamine 2 -methylpropanesulfonic acid and its salt, and a phosphate group by making PHOSMER-M, PHOSMER-PE, etc. (UN I - C Η Μ Μ I CAL (manufactured by CAL) is a copolymer of phosphoric acid or a salt thereof. In the above alkali-soluble group, a carboxyl group, a sulfonic acid group, a phosphoric acid group or an imide group is preferred, and a carboxyl group is particularly preferred. The above alkali-soluble group can be introduced by a high molecular reaction. Further, in order to increase the film strength of the image portion, the alkali-soluble binder polymer can be crosslinked as described above. In order to impart crosslinkability to the binder polymer, a crosslinkable functional group such as an ethylenically unsaturated bond may be introduced into the main chain or in the side chain of the polymer. The crosslinkable functional group can be introduced by copolymerization or by a polymer reaction. The mass average molecular weight of the alkali-soluble binder polymer is preferably 5,000 to -45-200819915, preferably 10,000 to 30,000, and the number average molecular weight is preferably 1000 or more, and 2000 to 250,000. More preferably, the polydispersity (mass average molecular weight / number average molecular weight) is preferably 1. idO. The alkali-soluble binder polymer may be any of a random polymer, a block polymer, and a graft polymer, and a random polymer is preferred. The soluble binder polymer may be used singly or in combination of two or more. The content of the alkali-soluble binder polymer is usually from 5 to 90% by mass based on the total solid content of the photosensitive layer, preferably from 10 to 70% by mass, more preferably from 10 to 60% by mass. In this range, good image portion strength and image formation properties can be obtained. (D-2) Hydrophobic binder polymer having an acid value of 〇.3 meq/g or less is subjected to development processing in a plate making step, and is carried out using a developing solution of pH 2 to 10 to have an acid value of 0.3 me. A hydrophobic binder polymer of q/g or less is preferred. The hydrophobic binder polymer having an acid value of 0.3 meq/g or less is preferably a water-insoluble polymer. Further, it is preferred that the acid group such as a carboxyl group, a sulfonic acid group or a phosphoric acid group is not substantially contained. The acid value of the hydrophobic binder polymer is the chemical equivalent number of the polymer per gram of acid. The acid value of the hydrophobic binder polymer is preferably 〇.lmeq/g or less. That is, the hydrophobic binder polymer is preferably insoluble in an aqueous solution of pH 2 to 10. The amount of the hydrophobic binder polymer dissolved in an aqueous solution of pH 2 to 10 is preferably 0.5% by mass or less, more preferably 0.1% by mass or less. By using such a hydrophobic binder polymer, the photosensitive layer can be improved in film strength from -46 to 20081991, water resistance, and meatiness, thereby improving the printing durability. The hydrophobic adhesive polymer is preferably a linear organic polymer having a film property, as long as it does not impair the performance of the lithographic printing plate of the present invention, and it is preferably in the above range, and a conventionally known one can be used without limitation. Examples of such a hydrophobic binder polymer are selected from the group consisting of acrylic resins, polyvinyl acetal resins, polyurethane resins, polyamide resins, epoxy resins, methacrylic resins, and styrene resins. The Φ polymer of the polyester resin is preferred. Among them, an acrylic resin is preferred, and a (meth) acrylate copolymer is preferred. More specifically, the alkyl (meth) acrylate or aralkyl ester, and the ester residue (-COOR) of the (meth) acrylate contain -CH2CH20-unit or -CH2CH2NH-unit (methyl) Acrylate copolymers are particularly preferred. The alkyl group of the above (meth)acrylic acid ester is preferably an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group. The aryl (meth)acrylate is preferably benzyl (meth)acrylate. Further, in order to increase the film strength of the image portion, the hydrophobic adhesive φ agent polymer may have crosslinkability as described above. In order to impart crosslinkability to the hydrophobic binder polymer, a crosslinkable functional group such as an ethylenically unsaturated bond may be introduced into the side chain. The crosslinkable functional group can be introduced by copolymerization or can be introduced by a polymer reaction. Further, from the viewpoint of improving the developability of the aqueous solution, the binder polymer is preferably hydrophilic, and the binder polymer has a good phase with the polymerizable compound contained in the photosensitive layer from the viewpoint of improving the printing durability. The solubility is important, that is, it is preferably lipophilic. From such a viewpoint, in order to improve the developability and the printing durability, the present invention is also effective in copolymerizing a hydrophilic group -47-200819915 in a hydrophobic binder polymer with a lipophilic group. Examples of the hydrophilic group include a hydroxyl group, a carboxylate group, a hydroxyethyl group, a vinyloxy group, a hydroxypropyl group, a polyoxyethyl group, a polyoxypropyl group, an amine group, an aminoethyl group, an aminopropyl group, and an ammonium group. A substance having a hydrophilic group such as a thiol group or a carboxymethyl group is preferred. The hydrophobic binder polymer preferably has a mass average molecular weight of 5,000 or more, more preferably 10,000 to 30,000, and a number average molecular weight of preferably 1,000 or more, more preferably 20,000 to 250,000. The polydispersity (mass average molecular weight / number average molecular weight) is preferably from 1.1 to 10. The hydrophobic binder polymer may be any of a random polymer, a block polymer, a graft polymer, etc., preferably a random polymer. The hydrophobic binder polymer may be used singly or in combination of two or more. The content of the hydrophobic binder polymer is usually from 5 to 90% by mass, more preferably from 10 to 70% by mass, even more preferably from 10 to 60% by mass, based on the total solid content of the photosensitive layer. Within this range, good image portion strength and image formation properties can be obtained. (Common sensitizer) By using an additive, the sensitivity of the photosensitive layer can be further improved. Such a compound is referred to as a co-sensitizer in the present invention. These mechanisms of action are not clear, and it is believed that most of them are based on the following chemical steps. That is, it is presumed that a photoreaction is generated by the light absorption of the photopolymerization initiator described above, and then various intermediate active species (free radicals, peroxides, oxides, reducing agents, etc.) generated by the addition polymerization reaction are The co-sensitizer reacts to produce new active free radicals. Mostly, it can be classified into (a) a substance which is reduced to produce an activity-free radical -48-200819915; (b) a free radical reaction which is oxidized to generate an active radical and has a low physical activity, and the freedom to be converted into a high activity is The role of the chain transfer agent, with regard to the respective compound system, most of them do not have a common statement. (a) A substance which is reduced to produce an active radical. A compound having a carbon-dentate bond. It is considered that carbon-dentate is broken to generate an active radical. Specifically, for example, a triad or a trihalomethyloxadiazole can be suitably used. A compound having a nitrogen-nitrogen bond: It is considered that the nitrogen-nitrogen bond is also broken to generate an active radical. Specifically, for example, a hexaaryl group can be suitably used. Compound V having an oxygen-oxygen bond: It is considered that the nitrogen-nitrogen bond is also broken to generate an active radical. Specifically, for example, organic is suitable for use. Key compound: It is considered that a carbon-hetero bond or an oxygen-nitrogen bond is also broken to generate an active radical. Specifically, for example, a diaryltriarylsulfonium salt or an N-alkoxypyridylium salt (吖 钥 key) is used in combination. Di(cyclopentadienyl) ferrous iron, iron aromatic iron complex: to form active free radicals. (b) A substance which is oxidized to generate an active radical. The alkylate complex: It is considered that the carbon-hetero bond is oxidized to form an active radical. Specifically, for example, a triarylalkyl borate is used. And (c) an iodine-producing iodine-producing salt such as a divalent imidazole, such as a diimidazole, which is produced by a reactive group or a reactive group, or a halogenated methyl-S-trimer Class, class, etc. capable of reducing reductive cleavage, class, etc. -49 - 200819915 Alkylamine compound: It can be considered to be active by oxidizing the c-χ bond on the carbon adjacent to nitrogen. Free radicals. The hydrazine is preferably a hydrogen atom, a carboxyl group, a trimethyldecyl group, a benzyl group or the like. Specifically, for example, an ethanolamine, a fluorenyl-phenylglycine, a ruthenium-trimethyldecylmethylaniline, etc., a sulfur-containing tin-containing compound: a sulfur atom or a tin atom is substituted for the nitrogen atom of the above amine. The object, by the same action, can generate active free radicals. Further, it is known that a compound having an S - S bond can also be sensitized by S - S cleavage. The α-substituted methylcarbonyl compound: an active radical can be formed by oxidation and cleavage by a bond between carbonyl and α carbon. Further, the product obtained by converting a carbonyl group into an oxime ether has the same effect. Specific examples thereof include 2-benzine-1 - [ 4 -(indolylthio)phenyl]-2-sodium phenylacetone-1, and examples thereof include the reaction of hydroxyamines with hydroxyamines. - Ether ethers obtained by etherification. Sulfinated salts: capable of reductively generating active radicals. Specifically, sodium arylsulfinate or the like can be given. (c) a radical which reacts with a radical to be converted into a highly active radical, or which acts as a chain transfer agent, reacts with a radical, converts into a radical having a high activity, or acts as a chain transfer agent, for example, can be used, for example. A group of compounds having SH, PH, SiH, and GeH in the molecule. In this case, hydrogen is supplied to a low-activity radical species to generate a radical, or after being oxidized, a free radical can be generated by deprotonation. Specific examples thereof include 2-hydroxythiobenzimidazoles and the like. More specific examples of such co-sensitizers are, for example, those disclosed in Japanese Laid-Open Patent Publication No. Hei 9-23 69 1 3 for the purpose of improving sensitivity, and the addition of 50-200819915. Some examples are given below, but the present invention is not limited thereto.

These co-sensitizers can be further modified in accordance with the characteristics of the photosensitive layer of the original plate of the printing plate as in the case of the conventional co-sensitizer. For example, it is possible to introduce a hydrophilic component, a hydrophilicity-promoting moiety, a substituent which inhibits crystallization, and a substituent which is used for extracting, by introducing a partial bond with a sensitizing coloring matter, an initiator, and a polymerization radical. And methods such as polymerization. These co-sensitizers may be used in combination of two or more kinds. The amount of use is 〇 with respect to 100 parts by mass of the polymer having an ethylenically unsaturated double bond. 〇 5 to 100 parts by mass, preferably in parts by volume, more preferably in the range of 3 to 50 parts by mass. (Microcapsule) In the present invention, a method of containing the photosensitive layer structural component and other structural components in the photosensitive layer, for example, can be described in JP-A-2001, JP-A-200-277742 The glue has a portion of the structural component and is added to the photosensitive layer. At this time, each component can be contained in the microcapsules and outside the microcapsules at an arbitrary ratio. Improved flat chemical modification and incorporation for adhesion or adhesion alone or in combination 1 to 80. 277740 capsular inclusion structure described later -51- 200819915 The method of microencapsulation of the photosensitive layer structural component can be carried out by a well-known method. For example, the method for producing a microcapsule can utilize the coagulation method described in the specification of U.S. Patent No. 2,080, 045, and the specification of U.S. Patent No. 2,048, 854; the specification of U.S. Patent No. 3,287,54, the disclosure of which is incorporated herein by reference. An interfacial polymerization method described in each of the '446 publications; a method for precipitating a polymer according to the specification of U.S. Patent No. 3,418,250, and the specification of No. 3,606,04; according to U.S. Patent No. 3 7 9 Method for the isocyanate polyol wall material of 6 6 6 9; method for isocyanate polyol wall material of US Pat. No. 3 9 1 4 5 1 1; each specification of the US Patent No. 4 0 0 1 1 0 0 Method for forming a urea-formaldehyde or urea-formaldehyde-resorcin-based wall forming material according to the specification of No. 4 0 8 7 3 7 6 and the same as No. 4 0 8 9 8 2; US Patent No. 4025445 a method of using a wall material such as melamine-formaldehyde resin or hydroxycellulose; in situ in the polymerization of a monomer described in each of the publications of Japanese Patent Publication No. Sho 3-6-9 1 63 Law; and British Patent No. 9 3 0 4 2 2, US Patent No. 3 1 The spray drying method described in the specification of 1 1 4 0 7; and the electrolytic dispersion cooling method described in each of the specifications of the British Patent No. 9 5 2 8 7 and the same as 9 067 074; however, the present invention is not limited thereto. . The preferred microcapsule wall system used in the present invention has three-dimensional cross-linking properties which are swelled by a solvent. From this point of view, the wall material of the microcapsules is preferably polyurea, polyurethane, polyester, polycarbonate, polyamine and mixtures thereof, and is characterized by polyurea and polyurethane. good. Further, a compound having a crosslinkable functional group such as an ethylenically unsaturated bond capable of introducing the above-mentioned water-insoluble polymer may be introduced into the microcapsule wall. -52- 200819915 The average particle size of the above microcapsules is 0. 01~3. 0 micron is preferred. With 0. 05~2. 0 micron is better, to 〇. 1〇~1. 〇Micron is especially good. Within this range, good resolution and stability over time can be obtained. (Other photosensitive layer components) The photosensitive layer of this invention can contain various additives as needed. Hereinafter, the description will be made. (Surfactant) In the present invention, in order to promote the developability and to enhance the coating surface, it is preferred to use a surfactant in the photosensitive layer. Examples of the surfactant include a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a fluorine-based surfactant. The surfactants may be used singly or in combination of two or more. The nonionic surfactant to be used in the present invention is not particularly limited, and those previously known can be used. Examples thereof include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene polystyrene phenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, and glycerin fatty acid partial esters. , sorbitan fatty acid partial esters, neopentyl alcohol fatty acid partial esters, propylene glycol mono- fatty acid partial esters, sucrose fatty acid partial esters, polyoxyethylene sorbitan fatty acid partial esters, polyoxyethylene sorbitol Fatty acid partial esters, polyethylene glycol fatty acid partial esters, polyglycerol fatty acid partial esters, polyoxyethylated castor oils, polyoxyethylene glycerol fatty acid partial esters, fatty acid diethanolamines, hydrazine, hydrazine-double a copolymer of a -2-hydroxyalkylamine, a polyoxyethylene alkylamine, a triethanolamine fatty acid partial ester, a trialkylamine oxide, a polyethylene glycol, a polyethylene glycol, and a polypropylene glycol. -53- 200819915 The anionic surfactant used in the present invention is not particularly limited. It is possible to use a previously known one. For example, a fatty acid salt, a rosin acid salt, a hydroxy alkane sulfonate, an alkane sulfonate, a two-yard sulfonic acid succinate salt, a linear alkylbenzene sulfonate, etc. are mentioned. Branch chain-based besylate, alkylnaphthalene sulfonate, alkylphenoxy polyoxyethylene propyl sulfonate, polyoxyethylene alkyl sulfonate phenyl ether salt, N- Methyl sulfonium sulfonate sodium salt, N-alkyl sulfosuccinate monoamine sulphate disodium salt, petroleum sulfonic acid 0 salt, sulfated tallow oil, fatty acid alkyl ester sulfate salt, alkane Sulfate salts, polyoxyethylene alkyl ether sulfate salts, fatty acid monoglyceride sulfate salts, polyoxyethylene alkylphenyl ether sulfate salts, polyoxyethylene styryl phenyl ether sulfate a salt, an alkyl phosphate salt, a polyoxyethylene alkyl ether phosphate salt, a polyoxyethylene alkylphenyl ether phosphate salt, a partial saponified product of a styrene/maleic anhydride copolymer, Partial saponification of olefin/maleic anhydride copolymer, naphthalene sulfonate fumarin condensate φ anionic surfactant used in the present invention It is not particularly limited, and previously known things can be used. For example, alkylamine salts, fourth-order ammonium salts, polyoxyethylene alkylamine salts, and polyethylene polyamine derivatives can be mentioned. The amphoteric surfactant is not particularly limited as long as it is known in the art. For example, a carboxybetaine, an aminocarboxylic acid, a sulfobetaine, an amine sulfate, and an imidazole are mentioned. Further, among the above-mentioned surfactants, those having "polyoxyethylene" may be replaced by "polyoxymethylene", such as polyoxymethylene, polyoxypropylene or polyoxybutylene. These surfactants can be used. -54- 200819915 A more preferred surfactant is a fluorine-based surfactant containing a perfluoroalkyl group in the molecule. Examples of such a fluorine-based surfactant include anionic forms such as perfluoroalkyl carboxylate, perfluoroalkylsulfonate, and perfluoroalkyl phosphate; and amphoteric types such as perfluoroalkylbetaine; perfluoroalkane; a cationic type such as a trimethylammonium salt; an oxidized perfluoroalkylamine, a perfluoroalkyl ethylene oxide adduct, an oligomer containing a perfluoroalkyl group and a hydrophilic group, a perfluoroalkyl group, and a lipophilic group An oligomer, a perfluoroalkyl group, a hydrophilic and lipophilic group-containing oligomer, and a non-ionic type such as a fluoroalkyl group and an oleyl group-containing urethane. Further, a fluorine-based surfactant described in JP-A-62-17050, JP-A-62-226 1 43 and JP-A-60-168144 can also be used. The surfactant may be used alone or in combination of two or more. The content of the surfactant is preferably 0.0000 to 10% by mass, based on the total solid content of the photosensitive layer. 0^7% by mass is more preferable. (Colorant) In the present invention, a dyeing material having a large absorption in the visible light region can be used as the image coloring agent. Specifically, oil-soluble yellow #1 0 1 , oil-soluble yellow #1 0 3, oil-soluble pink # 3 1 2, oil-soluble green BG, oil-soluble blue Β 、 S, oil-soluble blue # 6 0 3, oil Soluble black Β γ, oil-soluble black b S, oil-soluble black T-5 05 (made by ORIENT Chemical Industry Co., Ltd.), Victoria blue, crystal violet (C142555), methyl violet (CI42535), A dye described in JP-A-62-293247, such as ethyl violet, rhodamine B (CI 145170B), malachite green (C142 000), methylene blue (C152015), and the like. Further, pigments such as indigo pigments, azo pigments, carbon black, and titanium oxide are also suitably used. -55- 200819915 Since these colorants can be easily added to the area image portion and the non-image portion after image formation, it is preferable to add them. In addition, the total solid content of the photosensitive layer is added in an amount of 〇.  〇 1 to 1 〇 mass% ratio is better. (Printing agent) In order to produce a print image, a compound which is discolored by an acid or a radical can be added to the photosensitive layer of the present invention. Such compounds are various colors such as diphenylmethane, triphenylmethane, thioline, lanthanum, xanthene, anthraquinone, imine lanthanide, azo, and carbamide. The material can be used effectively. Specific examples thereof include brilliant green, ethyl violet, methyl green, crystal violet, basic magenta, methyl violet 2B, quinaldine red, rose red, mitane yellow, rivastyl sulfonate, and Cresol blue, methyl orange, p-methyl red, Congo red, Benzo red purple 4B, α-naphthyl red, Nile blue 2B, Nile blue A, methyl violet, malachite green, vice magenta, Victoria Pure blue · BOH [HODOGAYA (share) system], oil soluble blue #603 [ORIENT chemical industry (share) system], oil soluble pink.  #3 12 [ORIENT Chemical Industry Co., Ltd.], oil-soluble red 5B [ORIENT Chemical Industry Co., Ltd.], oil-soluble red #308 [ORIENT Chemical Industry Co., Ltd.], oil-soluble red 〇G[ORIENT chemistry Industrial (stock) system], oil-soluble red RR [ORIENT Chemical Industry Co., Ltd.], oil-soluble green #5 02 [ORIENT Chemical Industry Co., Ltd.], SPIRON RED BEH SPECIAL [HODOGAYA (share) system], Cresol purple, cresol red, rhodamine B, rhodamine 6G, sulfonyl rhodamine B, alamin, 4-p-diethylaminophenylimino naphthoquinone, 2-carboxyanilinyl 4-p-diethylaminophenyliminonaphthylquinone, 2-carboxystearylamino-4-p-N,N-bis(hydroxyethyl)amino-phenylimidonaphthalene醌, 1-phenyl-56- 200819915 -3-methyl-4-p-diethylaminophenylimido-5-pyrazolone, 1-β·naphthyl p-diethylaminophenylimine A dye such as keto-5-pyrazolone or a leuco dye such as hydrazine, Ρ', ρ'$ methyltriaminetriphenylmethane (colorless crystal violet) or Pergascript BUe SRB (manufactured by CIBAGEIGY Co., Ltd.). In addition to the above, a leuco dye which is known as a raw material for thermal paper or sensation paper can be suitably used. Specific examples thereof include crystal violet lactone, malachite green lactone, benzamidine leuco methylene blue, and 2-(N-phenyl-N-methylamino)-6-(N-p-tolyl-N-B Amino-fluorescein yellow mother, 2-anilino_3_methyl-6-(N-ethyl-p-toluidine) fluorescent yellow mother, 3,6-dimethoxy fluorescent yellow mother, 3-(Ν,Ν·diethylamino)-5-methyl-7-(N,N-dibenzylamino)·fluorescent yellow mother, 3-(N-cyclohexyl-N-methylamino) -6-methyl-7-anilinyl fluorescent yellow mother, 3-(N,N-diethylamino)-6-methyl-7-anilinyl fluorescent yellow mother, 3-(N,N-di Ethylamino)-6-methyl-7-dimethylanilinyl fluorescent yellow mother, 3-(N,N-diethylamino)-6-methyl-7-chlorofluorescent yellow mother, 3- (N,N-diethylamino)-6-methoxy-7-aminofluorescent yellow precursor, 3-(N,N-diethylamino)-7-(4-chloroanilino)fluorescence Yellow mother, 3-(N,N-diethylamino)-7-chlorofluorescent yellow mother, 3-(N,N-diethylamino)-7-benzylamine fluorescent yellow mother, 3- (N,N-diethylamino)-7,8-benzoquinone fluorescent yellow mother, 3-(N,N-dibutylamino)-6-methyl-7-anilinyl fluorescent yellow mother, 3 -(N,N-dibutylamino -6-methyl-7-dimethylanilinyl fluorescent yellow mother, 3-piperidinyl-6-methyl-7-phenyl-amine-fluorescent yellow mother, 3-pyrrolidinyl-6-methyl -7-anilinofluorescent yellow mother, 3,3-bis(1-ethyl-2-methylindol-3-yl)decanolactone, 3,3-bis(1-n-butyl-2· Methyl indol-3-yl) azlactone, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminodecanolide, 3-(4-diethylamino-2 -ethoxyphenyl)-3-(1-ethyl-2-methylindole-57- 200819915 -3-yl)-4-decalactone, 3-(4-diethylaminophenyl) -3-(1-ethyl-2-methylindol-3-yl)decanolactone and the like. The amount of the dye which is discolored by acid or radical is added to the solid content of the photosensitive layer by 0. 0 1 to 1 5 mass% is preferred. (Polymerization inhibitor) In order to prevent unnecessary thermal polymerization of the polymerizable compound during the production or storage of the photosensitive layer, it is preferred to add a small amount of the heat-resistant polymer to the photosensitive layer of the present invention. The heat-resistant polymerization agent may, for example, be hydroquinone, p-methoxy-phenol, di-tert-butyl-p-cresol, gallic phenol, tert-butyl phenol, p-benzoquinone or 4,4-thiobis ( 3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6.t-butylphenol), N-nitroso-N-phenylhydroxylamine Aluminum salt is preferred. For the solid content of the photosensitive layer, the amount of the anti-heating polymerization agent is about 〇. 〇1~ About 5 mass% is preferred. (higher fatty acid derivative or the like) In order to prevent polymerization inhibition by oxygen, a higher fatty acid derivative such as rosin or rosin may be added to the photosensitive layer of the present invention, and the drying step after coating may be partially biased. The surface of the photosensitive layer. The amount of the higher fatty acid derivative to be added is preferably from about 1 to about 10% by mass based on the solid content of the photosensitive layer. (Plasticizer) The photosensitive layer of the present invention may also contain a plasticizer. The plasticizer may suitably be exemplified by dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, octyl octyl phthalate, dicyclohexyl phthalate. , tannic acid di--58- 200819915 tridecyl ester, butyl benzyl phthalate, diisononyl phthalate, diallyl phthalate, etc.; dimethyl glycol phthalate, ethanol Glycol esters such as ethyl ethyl decyl ethyl ester, methyl decyl ethyl glycol glycolate, butyl decyl butyl glycolate, and triethylene glycol dicaprylate; tricresyl phosphate, triphenyl phosphate Phosphates such as esters; diisobutyl adipate, dioctyl adipate, dimethyl sebacate, dibutyl sebacate, dioctyl sebacate, dibutyl maleate The aliphatic dibasic acid esters are poly(butyl methacrylate), triethyl citrate, triacetin, butyl laurate and the like. The content of the plasticizer is preferably 30% by mass or less based on the solid content of the photosensitive layer. (Inorganic Fine Particles) The photosensitive layer of the present invention may contain inorganic fine particles in order to increase the strength of the cured film of the image portion. The inorganic fine particles may suitably be a mixture of, for example, cerium oxide, aluminum oxide, magnesium oxide, titanium oxide, magnesium carbonate, alginic acid or the like. Although these have no photothermal conversion property, it is also possible to enhance the interfacial adhesion by strengthening the film and roughening the surface. The average particle diameter of the inorganic fine particles is preferably from 5 nm to 10 μm, and is 0. 5 to 3 microns is better. When it is in the above range, it can be stably dispersed in the photosensitive layer, and the film strength of the photosensitive layer can be sufficiently maintained, and a non-image portion excellent in hydrophilicity which is less likely to cause contamination during printing can be formed. The above inorganic fine particles can be easily obtained from a commercially available product of a colloidal ceria dispersion. The content of the inorganic fine particles is preferably 20% by mass or less, more preferably 1% by mass or less, based on the solid content of the photosensitive layer. (Low-Molecular Hydrophilic Compound) -59- 200819915 In order to improve developability, a hydrophilic low molecular compound can be contained in the photosensitive layer of the present invention. Examples of the hydrophilic low molecular compound such as a water-soluble organic compound include glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, and triethylene glycol, and ethers or ester derivatives thereof. , such as polyhydric acids such as glycerin and neopentyl alcohol, organic amines such as triethanolamine and diethanolamine monoethanolamine, and salts thereof, sulfonic acids and salts thereof such as toluenesulfonic acid and benzenesulfonic acid, and organic sulfonic acids such as phenylsulfonic acid. And an organic carboxylic acid such as a salt, tartaric acid, oxalic acid, citric acid, malic acid, lactic acid, gluconic acid or amino acid, or a salt thereof, or an organic quaternary ammonium salt such as tetraethylamine hydrochloride. The photosensitive layer of the present invention may contain, for example, a co-sensitizer in addition to the above. (Formation of Photosensitive Layer) The photosensitive layer of the present invention is obtained by dispersing or dissolving the above-mentioned respective components in a solvent to prepare a coating liquid, and applying it. The solvent to be used herein may, for example, be ethylene dichloride, cyclohexanone, methyl ethyl ketone, methanol, ethanol, propanol, ethylene glycol monomethyl ether or 1-methoxy-2-propanol. 2-methoxyethyl acetate, methoxycarbonyl-2-propyl acetate, dimethoxyethane, methyl lactate, ethyl lactate, N,N-dimethylacetamide, N,N-dimethylformamide, V tetramethylurea, N-methyl fluorenone dimethyl hydrazine, butyl sulfonium, r-butyrolactone, toluene, water, etc. 'but not limited This is the case. These solvents may be used singly or in combination. The solid content concentration of the coating liquid is preferably from 1 to 50% by mass. The photosensitive layer of the present invention can also be formed by a plurality of times of preparing a coating liquid obtained by dispersing or dissolving the same or different components described above in the same or different solvents, followed by repeated application of a plurality of coatings. -60- 200819915 Further, the coating amount (solid content) of the photosensitive layer on the support obtained after coating and drying varies depending on the use, and is usually 〇. 3~3. 0 g / m ^ 2 is preferred. In this range, good sensitivity and good film properties of the photosensitive layer can be obtained. Various methods can be used for the coating method. For example, bar coating, spin coating, spray coating, curtain coating, dip coating, pneumatic blade coating, blade coating, roll coating, and the like can be given. [Protective layer] The lithographic printing plate precursor of the present invention can provide a protective layer (oxygen barrier layer) on the photosensitive layer in order to isolate the diffusion of oxygen which hinders the polymerization reaction at the time of exposure. The protective layer used in the present invention has an oxygen permeability A of 1. at 25 ° C and 1 atm. 0 € Ag 20 (ml/m2 • day) is preferred. Oxygen permeability A is less than 1.  The extremely low case of 0 (ml/m2 • day) will cause unwanted polymerization during manufacturing and before use, and will produce unwanted whitening and thicker image lines when the image is exposed. The problem. Conversely, an oxygen permeability A greater than 20 (ml/m2 • day) is too high, resulting in low sensitivity. Oxygen permeability A is 1 . 5 ‘ A S 12 (ml / square metric • day) range is better, to 2. 0 S AS 10. The range of 0 (ml / m ^ 2 · day) is better. Further, the required properties of the protective layer are not only the above-described oxygen permeability, but also excellent in the adhesion of the light used for the exposure and the adhesion to the photosensitive layer, and the development step after the exposure can be easily performed. Removal is better. The prior art of the present invention is described in detail in the specification of U.S. Patent No. 3,4,8,8,11, and Japanese Patent Publication No. 5-5-49279. -61- 200819915 The material which can be used for the protective layer is preferably a water-soluble polymer compound having excellent crystallinity, and specific examples thereof include polyvinyl alcohol, vinyl alcohol/ethylene phthalate copolymer, and vinyl acetate/vinyl alcohol. Water-soluble polymers such as vinyl phthalate copolymer, vinyl acetate/crotonic acid copolymer, polyvinylpyrrolidone, acid cellulose, gelatin, gum arabic, polyacrylic acid, polypropylene decylamine, etc., which may be used singly or in combination. . Among these, the use of polyvinyl alcohol as a main component' can provide more excellent basic characteristics of oxygen barrier properties and developmental removability. The polyvinyl alcohol used in the protective layer may be partially substituted with an ester, an ether or an acetal as long as it contains an unsubstituted vinyl alcohol unit having a necessary oxygen barrier property and water solubility. Further, similarly, a part may have other copolymerization components. Specific examples of the polyethylene include those having a degree of hydrolysis of 71 to 100 mol% and a polymerization repeating unit of 300 to 2400. Specifically, PVA-105, PVA-110, PVA-117, PVA-117H, PVA-120, PVA-124, PVA-124H, PVA-CS, PVA-CST, PVA-HC manufactured by Kuraray Co., Ltd. , PVA-2 0 3, PVA-204, P VA-2 0 5, PVA-210, PVA-217, PVA-220, PVA-224, PVA-217EE, PVA-217E, PVA-220E, PVA-224E, PVA-405, PVA-420, PVA-613, L-8, etc., these may be used alone or in combination. Preferably, the content in the protective layer of polyvinyl alcohol is 20 to 95% by mass, more preferably 30 to 9% by mass. Further, a well-known modified polyvinyl alcohol can also be suitably used. For example, an anion-modified portion which is modified by an anion such as a carboxyl group or a sulfonic acid group, and a cation which is modified by a cation such as an amine group or an ammonium group, and a cation-62-200819915 modified portion, a stanol a polyvinyl alcohol having various degrees of polymerization of various hydrophilic modified portions such as a modified portion and a thiol-modified portion; and the anion-modified portion, the cation-modified portion, and the stanol-modified portion at the terminal of the polymer chain , a mercaptan-modified portion, alkoxy-modified portion, a thioether-modified portion, an ester-modified portion of vinyl alcohol and various organic acids, an ester-modified portion of the anion-modified portion and an alcohol, and an epoxy Polyvinyl alcohol or the like having various degrees of polymerization of various modified sites such as a modified portion. The content of the polyvinylpyrrolidone or a modified product thereof as a component to be mixed with polyvinyl alcohol from the viewpoint of oxygen barrier property and developmental removability is 3. 5 to 80% by mass, preferably 10 to 60% by mass, more preferably 15 to 30% by mass. The composition of the protective layer (the selection of the PVA, the use of the additive), and the coating amount are selected in consideration of the whitening property, the adhesion property, and the abrasion resistance in addition to the oxygen barrier property and the image removal property. In general, the higher the hydrolysis rate of the PVA used (the higher the unsubstituted vinyl alcohol unit content in the protective layer) and the higher the film thickness, the higher the oxygen barrier property, which is advantageous in terms of sensitivity. The (co)polymer of the above polyvinyl alcohol (PVA) or the like may have a molecular weight of from 2,000 to 10,000,000, preferably from 20,000 to 30,000. As a other component of the protective layer, it is possible to add a certain amount of glycerin, dipropylene glycol, or the like to the (co)polymer to impart flexibility, and to add a mass% to the polymer compound binder. Anionic surfactant such as sodium alkyl sulfate as alkylsulfonate; amphoteric surfactant such as alkylaminocarboxylate or alkylaminodicarboxylate; and nonionic interfacial activity such as polyoxyethylene alkylphenyl ether Agent. -63- 200819915 Moreover, the adhesion to the image portion or the scratch resistance is extremely important in the processing of the printing plate. In other words, when the hydrophilic layer composed of the water-soluble polymer is laminated on the lipophilic photosensitive layer, film peeling is likely to occur due to insufficient adhesion, and the peeling portion may cause defects such as poor film hardening due to polymerization inhibition of oxygen. In this case, various proposals have been made to improve the adhesion between these two layers. For example, in the hydrophilic polymer mainly composed of polyvinyl alcohol, 20 to 60% by mass of acrylic acid is mixed in the hydrophilic polymer mainly composed of polyvinyl alcohol, as described in U.S. Patent Application No. 2,902, 510, and U.S. Patent Application Serial No. An emulsion or a water-insoluble vinylpyrrolidone-vinyl acetate copolymer or the like can be sufficiently laminated by laminating on a photosensitive layer. Any of these well-known techniques can also be applied to the protective layer of the present invention. The coating method of such a protective layer is described, for example, in the specification of U.S. Patent No. 3,458,311 and Japanese Patent Publication No. 55-49729. Further, in order to enhance the oxygen barrier property or the surface protective property of the photosensitive layer, the protective layer of the lithographic printing plate precursor of the present invention preferably contains an inorganic layered compound. Here, the inorganic layered compound has particles having a thin plate shape, and examples thereof include the following general formula A (B, C) 2-5D4 〇 10 (〇H, F, O) 2 (where A Any of K, Na, and Ca, natural mica represented by either B or C, Fe(II), Fe(III), Μη, Al, Mg, or V, D-based Si or Al) Mica group such as mica, talc represented by formula 3Mg0*Si0*H20, mica, montmorillonite, saponite, sodium mica, and chromium phosphate. In the above mica group, natural mica can be cited as muscovite, sodium mica, gold-64-200819915 mica, biotite and scale mica. Further, synthetic mica may be exemplified by fluorophlogopite KMg3 (AlSi301G) F2, potassium tetramica KMg2. 5 (Si401G)F2 and other non-swelling mica, and Na four mica NaMg2. 5(Si401())F2, Na or Li with mica (Na, Li) Mg2Li(Si4〇i〇)F2, montmorilloniteite system Na or Li needle sodastone (Na, Li) 1/8Mg2 Sweeping mica such as /5Li1/8 (Si4〇i())F2. Also, the synthesis of smectite (sumectite) is also useful. In the above-mentioned inorganic layered compound, the fluorine-based swellable mica which is a synthetic inorganic layered compound is particularly useful. That is, the swellable mica, or swellable clay such as montmorillonite, saponite, cannafeite, bentonite, etc. Minerals and the like have a laminated structure composed of a unit crystal lattice layer having a thickness of about 10 to 15 A, and the metal atom substitution system in the lattice is remarkably larger than other clay minerals. As a result, the lattice layer is deficient in positive charges, and cations such as Na+, Ca2+, and Mg2+ adsorbed between the layers in order to compensate. These inter-layer cations are called exchange cations and can be exchanged with various cations. In particular, in the case of the cations Li+ and Na+ between the layers, since the ionic radius is small, the bond between the intergranular crystal lattices is weak, and the swelling is increased by water. In this state, if shearing is applied, it is easy to crack and form a stable sol in water. The tendency of bentonite and swellable synthetic mica is strong, and it is useful in the present invention to use swellable synthetic mica. The shape of the inorganic layered compound used in the present invention is preferably as thin as possible from the viewpoint of diffusion control, and the planar size is preferably as long as it does not impede the smoothness of the coated surface or the transmittance of the active light. Therefore, the aspect ratio is 20 or more, preferably 100 or more, and particularly preferably 200 or more. Further, the ratio of the aspect ratio to the thickness of the long diameter of the particles can be measured, for example, from a projection of a micrograph of the particle -65-200819915. The greater the aspect ratio, the greater the effect. The particle size of the inorganic layered compound used in the present invention has an average length of 0. 3 to 2 0 micron, to 0. 5 to 10 μm is preferred, and 1 to 5 μm is preferred. Moreover, the average thickness of the particles is 0. Below 1 micron, to 0. Below 05 microns is better, to 〇.  〇 1 micron or less is especially good. For example, among the inorganic layered compounds, the swellable synthetic mica of the representative compound has a size of 1 to 50 nm and a face size of about 1 to 20 μm. When such an inorganic layered compound having a large aspect ratio is contained in the protective layer, since the coating film strength can be improved, oxygen and moisture can be effectively prevented from being transmitted, so that deterioration of the protective layer due to deformation or the like can be prevented, and It can be stored for a long period of time even under high-humidity conditions, and there is no deterioration in image formation property of the lithographic printing plate precursor due to humidity change, and it has excellent preservation stability. The mass ratio of the organic layer-like compound in the protective layer is preferably from 5/1 to 1/100, based on the amount of the binder used in the protective layer. When a plurality of inorganic layered compounds are used, the total amount of these inorganic layered compounds is preferably the above-mentioned mass ratio. Next, an example of a usual dispersion method of the inorganic layered compound used for the protective layer will be described. First, 5 to 10 parts by mass of a swellable layered compound (a preferred compound of the inorganic layered compound mentioned above) is added to 100 parts by mass of water, and then fully melted with water and swelled, Dispersion is carried out by a disperser. The dispersing machine used here can be exemplified by various types of honing machines which are mechanically directly applied to disperse, and high-strength shearing power. -66·200819915 Stirring type dispersing machine, which can impart high-intensity ultrasonic energy dispersion. Machine and so on. Specifically, a ball mill, a sand mill, a homogenizing honing machine, a colloid mill, a homogenizer, a dissolver, a homogenizer (p〇1ytr〇n), a homomixer, a homogenizer, and a homomixing can be mentioned. Mixer, Caddy honing machine, jet mixer, capillary emulsifier, liquid whistle, electromagnetic strain ultrasonic generator, emulsifying device with Pohlmann flute. The dispersion of the inorganic layered compound of 5 to 10% by mass which was dispersed by the above method was high in viscosity or gel, and the storage stability was extremely excellent. When the protective layer coating liquid is prepared by using the dispersion, it is preferably diluted with water and thoroughly stirred, and then blended with a binder solution. In the protective layer coating liquid, in addition to the inorganic layered compound, a well-known additive such as a surfactant for improving coatability or a water-soluble plasticizer for improvement may be added. Examples of the water-soluble plasticity include acrylamide, cyclohexanediol, glycerin, and sorbitol. Further, a water-soluble (meth)acrylic polymer may also be added. Further, in order to improve the adhesion to the photosensitive layer and the stability of the coating liquid over time, a well-known additive may be added. The protective layer coating liquid thus prepared is applied onto a photosensitive layer formed on a support, and dried to form a protective layer. The coating solvent may be appropriately selected from those related to the binder, and when a water-soluble polymer is used, it is preferred to use distilled water or purified water. The coating method of the protective layer is not particularly limited, and a well-known method such as the method described in the specification of the U.S. Patent No. 3,45, 311 or the Japanese Patent Publication No. 5-5-4 9729 can be applied. Specifically, for example, a doctor blade coating method, a pneumatic blade coating method, a gravure coating method-67-200819915 method, a roll coating method, a spray coating method, a dip coating method, a bar coating method, and the like can be given. The coating amount of the protective layer is preferably in the range of 〇·05 to 10 g/m 2 , and the range of 0·1 to 0·5 g/m 2 when the inorganic layered compound is contained. More preferably, when it does not contain an inorganic inorganic layered compound, it is 0. A range of 5 to 5 g/m 2 is more preferred. [Support] The support used in the lithographic printing plate precursor of the present invention is not particularly limited, and may be a plate-shaped hydrophilic support having a stable size. Examples thereof include paper, plastic (for example, polyethylene, polypropylene, polystyrene, etc.) laminated paper, metal sheets (for example, aluminum, zinc, copper, etc.), and plastic films (for example, diacetate fibers). , cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, nitrocellulose, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, poly A vinyl acetal or the like, a paper or a plastic film obtained by laminating or vaporizing the above metal. Preferred support members are polyester film and aluminum plate. Among them, aluminum sheets are preferred because of their good dimensional stability and relatively low cost. The aluminum plate has a pure aluminum plate, an alloy plate containing aluminum as a main component and containing a small amount of different elements, or a laminate of plastic on an aluminum or aluminum alloy film. All the different elements in the aluminum alloy are alizarin, iron, manganese, copper, magnesium, chromium, zinc, antimony, nickel, and chin. The content of the different element in the alloy is preferably 1% by mass or less. In the present invention, a pure aluminum plate is preferred, since the manufacture of completely pure is difficult in terms of refining technology, and therefore it may contain a small amount of different elements. The nameplate does not have a specific composition, and the well-known materials can be suitably used. The thickness of the support is from 0·1 to 0. 6 mm is better, with 0. 15~0. 4mm -68- 200819915 is better, with 0. 2~0. 3 mm is better. It is preferred to carry out surface treatment such as roughening treatment and anodizing treatment before using the aluminum plate. The surface treatment can improve the hydrophilicity and easily ensure the adhesion of the photosensitive layer to the support. Before the roughening of the nameplate, it is preferable to carry out degreasing treatment using a surfactant, an organic solvent, or an alkaline aqueous solution as needed to remove the calendered oil of the watch. The roughening treatment of the surface of the aluminum plate can be carried out by various methods, and examples thereof include mechanical roughening treatment and electrochemical graining treatment (chemical surface roughening treatment), chemical rough surface Treatment (chemically selecting the roughening treatment of the dissolved surface). As a method of mechanical graining treatment, a well-known method such as a ball honing method, a brush honing method, a sandblasting honing method, or a polishing honing method can be used. The method of electrochemical graining treatment can be carried out, for example, by alternating current or direct current in an electrolytic solution containing an acid such as hydrochloric acid or nitric acid. Further, a method of using a mixed acid described in JP-A-54-6 5 3 902 is also possible. The aluminum plate which has been roughened may be subjected to an etching treatment using an aqueous solution such as potassium hydroxide or sodium hydroxide as necessary, and may be anodized to improve wear resistance after the neutralization treatment as needed. deal with. The electrolyte used in the anodizing treatment of the aluminum plate can use various electrolytes which can form a porous oxide film. A mixed acid of sulfuric acid, hydrochloric acid, oxalic acid, chromic acid or the like can be usually used. The concentration of these electrolytes can be appropriately determined depending on the type of the electrolyte. Since the anodizing treatment conditions vary from -69 to 20081991 depending on the electrolyte used, it cannot be specified at a glance, usually at an electrolyte concentration of 1 to 8 ο mass % solution, liquid temperature 5 to 70 ° C, current The density is 5 to 60 A/dm 2 , the voltage is 1 to 100 V, and the electrolysis time is 1 sec. to 5 minutes. The amount of the anodized film formed is from 1 to 0 to 5. 0 g / m ^ 2 is better, to 1 . 5~4. 0 g/cm 2 is more preferred. Within this range, good printing durability and good scratch resistance in the non-image portion of the lithographic printing plate can be obtained. The support used in the present invention may be a substrate having an anodic oxide film which has been subjected to the above surface treatment, and may be appropriately selected as necessary in order to improve adhesion to the upper layer, hydrophilicity, contamination resistance, heat insulation, and the like. The micropore enlargement treatment, the micropore sealing treatment, and the surface immersion treatment on the surface containing a hydrophilic compound, etc., are described in JP-A-2001-253181, JP-A-2001-322365. Of course, the sealing treatment is not limited to the above description, and any method previously known can be used. In addition to vapor sealing, the sealing treatment can also perform a separate treatment of fluoric acid chromic acid, a sealing treatment by an aqueous solution containing an inorganic fluorine compound, a sodium fluoride treatment, a vapor sealing with potassium chloride, and a borrowing process. It is sealed by hot water. Among them, the sealing treatment by the aqueous solution containing the inorganic fluorine compound is preferably carried out by a water vapor sealing treatment and a sealing treatment by hot water. The hydrophilization treatment is an alkali metal citrate method described in the specification of U.S. Patent No. 2,7, 066, the disclosure of which is incorporated herein by reference. In this method, the support is immersed or electrolytically treated with an aqueous solution such as sodium citrate. In addition, there is a method of treating potassium fluorochromate treated by -70-200819915, which is described in Japanese Patent No. 3,276,868, the disclosure of which is incorporated herein by reference. The method of phosphonic acid treatment. When the support system of the present invention uses a support having insufficient surface hydrophilicity such as a polyester film, it is preferred to apply a hydrophilic layer to make the surface hydrophilic. The hydrophilic layer is coated with cerium, magnesium, aluminum, lanthanum, titanium, boron, lanthanum, tin, chromium, iron, vanadium, niobium, and the like, which are described in JP-A-2000-119. a hydrophilic layer composed of a coating liquid of an oxide of an at least one element of a transition metal or a colloidal solution of a hydroxide; or a method of crosslinking or simulating cross-linking of an organic hydrophilic polymer as described in JP-A-2002-79772 a hydrophilic layer of an organic hydrophilic matrix; or an inorganic hydrophilic matrix obtained by a sol-gel transformation consisting of hydrolysis, condensation reaction of polyalkoxydecane, titanate, chromate or aluminate The hydrophilic layer; or a hydrophilic layer composed of an inorganic thin film having a metal oxide-containing surface is preferred. Among them, a hydrophilic layer formed by coating a coating liquid containing a cerium oxide or a hydroxide colloid is preferred. Further, when a polyester film or the like is used as the support system of the present invention, it is preferred to provide an antistatic layer on the hydrophilic layer side or the opposite side or both sides of the support. When the antistatic layer is disposed between the support and the hydrophilic layer, it can contribute to the adhesion of the hydrophilic layer. As the antistatic layer, a polymer layer obtained by dispersing metal oxide fine particles or a matting agent described in JP-A-2002-7 97 72 can be used. When the support is, for example, an aluminum plate, the average center line roughness of the surface is 0. 10 to 1. 2 microns is preferred. Within this range, good adhesion to the photosensitive layer - 71 - 200819915, good brush resistance, and good non-contamination property can be obtained. Further, the color density of the support is a reflection concentration of 〇\1 5~〇·65. Within this range, good image formation properties and good plate correctness after development can be obtained by preventing halation during image exposure. [Undercoat layer] In the lithographic printing plate precursor of the invention, it is preferred to provide a primer layer containing a polymerizable group compound on the support. When the undercoat layer is used, the photosensitive layer is disposed on the undercoat layer. Since the undercoat layer can strengthen the adhesion between the support and the photosensitive layer in the exposed portion, and the photosensitive layer can be easily peeled off from the support in the unexposed portion, the developability can be improved. Specific examples of the undercoat layer include a decane coupling agent having an ethylenic double bond reactive group capable of addition polymerization described in JP-A-H08-282679, and JP-A-2-3 0444 1 An addition of a polymerized ethylene double bond reactive group of a phosphorus compound or the like. The compound which is particularly preferable is a polymerizable group such as methacrylic acid or an acrylic group, and a compound having a support adhesion such as a sulfonic acid group, a phosphoric acid group or a phosphate group. In addition to the polymerizable group and the support-adhesive group, a suitable compound may be a compound having a hydrophilicity-imparting group such as an epoxy group. The coating amount (solid content) of the undercoat layer is 0. It is preferably 1 to 100 mg/m 2 , preferably 1 to 30 mg/m 2 . [Hard Coating Layer] After the surface treatment is performed on the support or after the undercoat layer is formed, a hard coat layer may be provided on the back surface of the support as necessary. The organic polymer compound described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Or a coating layer composed of a metal oxide obtained by hydrolyzing and polycondensing an inorganic metal compound. Among them, the use of an alkoxy compound such as Si(OCH3)4, Si(〇C2H5)4, Si(OC3H7)4 or Si(OC4H9)4 is preferred because it is inexpensive and easily available. <Plate making method> In the plate making step of the lithographic printing plate precursor of the present invention, it is also possible to comprehensively heat the film before, during, and from exposure to development. By such heating, the image formation reaction in the photosensitive layer can be promoted, and the advantage of improving the sensitivity, the printing durability, and the sensitivity can be obtained. Further, for the purpose of improving image strength and brush resistance, it is also effective to perform overall post-heating or full-exposure of the image after development. It is preferred that the heating before the development is carried out under mild conditions of 150 ° C or lower. When the temperature is too high, there is a possibility that an unnecessary hardening reaction or the like may occur in the non-image area. On the one hand, the heating after development can take advantage of very strong conditions. The heat treatment is usually carried out in the range of 200 to 500 °C. When the temperature is low, sufficient image enhancement cannot be achieved. When it is too high, there is a problem that the support is deteriorated and the image portion is thermally decomposed. The exposure method of the lithographic printing plate precursor of the present invention can be carried out without any limitation using a well-known method. The wave of the light source is not particularly limited, and it is preferable to use a material of 3 奈 nm to 850 nm. Further, it is preferable to use a material of 350 nm to 450 nm, and specifically, an InGaN-based semiconductor laser is preferred. The exposure mechanism may be any of an inner roller mode, an outer roller mode, and a platform mode. Further, the photosensitive layer component of the present invention can be dissolved in neutral water or weakly alkaline water by using the highly water-soluble -73-200819915, and the lithographic printing plate of such a constitution can be mounted on a printing machine. The exposure-development method is performed on the machine. 3 5 0 to 45 0 nanometers can obtain laser light sources, and can use the following. Capable of using gas lasers: ion laser (3 64 nm, 351 nm, 10 mW to 1 W), Kr ion laser (3 6 5 nm, 351 nm, 10 mW ~ 1 W); He-Cd Ray Shot (441 nm, 325 nm, ImW ~ 100 W), solid laser Nd : YAG (YV 〇 4) and SHG crystallization χ 2 times combination (355 nm, 5 mW ~ 1 W), Cr : LiSAF and SHG Combination of crystals (43 0 nm, l〇mW); KNb03 ring resonator of semiconductor laser system (43 0 nm, 30 mW), combination of waveguide type wavelength conversion element and AlGaAs, InGaAs semiconductor (380 nm ~ 450 nm, 5 mW to 100 mW), combination of waveguide type wavelength conversion element and AlGalnP, AlGaAs semiconductor (300 nm to 350 nm, 5 mW to 100 mW), AlGaInN (350 nm to 450 nm, 5 mW ~ 100 mW), and pulsed laser N2 laser (3 3 7 nm, pulse 〇 · 1 ~ 10 mJ), XeF (351 nm, pulse 10 ~ 250 mJ). Among these, from the wavelength characteristics and the cost surface, AlGalnN semiconductor lasers (for example, InGaN-based semiconductor lasers of 400 to 410 nm and 5 to 30 mW) are particularly preferable. Further, in the lithographic printing plate exposure apparatus of the scanning exposure method, the exposure mechanism has an inner roller method, an outer roller method, and a platform method, and all of the light sources other than the pulse laser light source can be used as the light source. Due to the relationship between sensory sensitivity and plate making time in reality, the following exposure devices are preferred. • Internal drum mode and use 1 gas laser or solid laser light source -74-

(eq3) 200819915 Single beam exposure apparatus • Platform mode and using a plurality of (10 or more) semi-guide beam exposure devices • External roller method and using a plurality of (10 or more) half-multibeam exposure devices as described above Laser direct-printing lithographic printing plate, sensitivity X (J/cm 2 ), exposure surface s of the sensing material (power q (W) of the square illuminating source, laser η, total exposure time (eq 1) ) is established. X*S = n*q*t (eql) i) In the inner drum type (single beam) mode, the number of revolutions of the laser f (radian/second), the sub-scan of the sense material, and the resolution Z ( Point / cm), total exposure time t (seconds) is established. f#Z#t =Lx (eq2) 11) In the outer drum type (multi-beam) mode, the number of laser rotations F (radians/second), the sub-scanning points of the materials, and the resolution Z (points/cm), The total exposure time t (seconds) and the relationship (eq 3 ) are established. F*Z*n*t = Lx

Hi) In the platform type (multi-beam) mode, the number of rotations of the polygon mirror H (radians/second), the sub-sweep of the sense material), the resolution Z (points/cm), and the total exposure time t (seconds). The formula (eq 4 ) is established. The multi-conductor laser of the body laser is often in the sense of sensitive material), the length of one ray t (seconds), the length Lx (the equation between the public (eq 2 ), the length Lx (the number of the beam (η) g length Lx (number of beamlets (η) -75 - 200819915 (eq4)

H*Z*n*t = L The required resolution (25 6〇dpi), plate size (Al/B 1, sub-scan length 42 inches), and exposure conditions of 2 / / hour for the actual printing plate. When the lithographic characteristics of the lithographic printing plate precursor of the present invention (photosensitive wavelength sensitivity: about 0.1 mJ/cm 2 ) are substituted into the above formula, it can be understood that the lithographic printing plate precursor of the present invention is combined with a semiconductor laser multiple beam exposure device. Time is better. Further, from the viewpoint of multiplication by operability, cost, and the like, it is preferable to combine with a semiconductor laser multi-beam exposure apparatus of an outer drum type. Further, for other exposure light of the lithographic printing plate precursor of the present invention, mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, visible and ultraviolet light of ultra high pressure, high pressure, medium pressure and low pressure may also be used. Various laser lights, fluorescent lights, tungsten lights, sunlight, etc. [Development] After the lithographic printing plate precursor image of the present invention is exposed, the protective layer and the photosensitive layer of the non-exposed portion are removed by using a developing solution, whereby an image can be formed on the surface of the hydrophilic support. The developing solution suitable for use in the present invention can be classified into (1) a substance having a ρ Η of 10 or more and (2) an aqueous solution having a p Η of 2 to 10. As described above, when the developing solution of (1) is used, the binder polymer used in the photosensitive layer is preferably an alkali-soluble binder, and when the developing solution (2) is used, the acid value is 〇.3meq. A hydrophobic binder polymer of /g or less is preferred. A developing solution having a pH of 10 or more suitable for use in the present invention will be described. The imaging liquid having a pH of 10 or more is, for example, sodium strontium-sodium, potassium citrate, hydrogen-oxygen-76-200819915, sodium hydride, potassium hydroxide, lithium hydroxide, sodium trisphosphate, sodium diphosphate, and ammonium phosphate. An aqueous alkaline agent such as a second-generation ammonium phosphate, a sodium metasilicate, a sodium hydrogencarbonate or an aqueous ammonia, or an aqueous solution of an organic alkaline agent such as monoethanolamine or diethanolamine is preferred. The pressure can be increased so that the concentration of the alkali solution is from 0. 1 to 10% by mass, preferably from 0.5 to 5% by mass. Further, in such an alkaline aqueous solution, an interface active agent or an organic solvent such as benzyl alcohol, 2-phenoxyethanol or 2-butoxyethanol may be contained in a small amount as necessary. For example, the contents described in the specification of U.S. Patent No. 3,357,591, and the specification of the Japanese Patent No. 3,615,040. From the viewpoint of having both the handleability and the developing liquid, the developing liquid having a pH of 10 or more is preferably in the range of pH 10 to 14, and more preferably in the range of pH 11 to 13. Another developing solution suitable for use in the present invention is an aqueous solution having a pH of 2 to 10. For example, an aqueous solution containing water alone or with water as a main component (water content of 60% by mass or more) is preferred, and an aqueous solution having the same composition as commonly known dampening water, containing a surfactant (anionic, nonionic) An aqueous solution of a system or a cationic system 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 preferred. The p Η of the developing solution is preferably 3 to 8 and more preferably 4 to 7. The components which can be contained in each of the developing liquids of the above (1) and (2) are as follows. Examples of the anionic surfactant used in the developing solution of the present invention include fatty acid salts, rosin acid salts, hydroxyalkanesulfonates, alkane-77-200819915 sulfonates, and dialkyl groups. Sulfonic succinates, linear alkyl benzenes, branched alkyl benzene sulfonates, alkylnaphthalene sulfonates, alkyl polyoxyethylene propyl sulfonates, polyoxyethylene hydrides Base sulfonate benzenes, N-methyl-N-oil sulfonyl taurine sodium, N-alkyl sulfosuccinate disodium salt, petroleum sulfonates, sulfated castor oil, sulfur Fatty oil, sulfate ester of fatty acid alkyl ester, alkyl sulfate ester oxyethylene alkyl ether sulfate salt, fatty acid monoglyceride sulfate polyoxyethylene alkyl phenyl ether sulfate salt, polyoxyethylene benzene Vinyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether salts, polyoxyethylene alkylphenyl ether phosphates, partial saponates of styrene-cis anhydride copolymers, olefins - Maleic anhydride co-partial saponified compounds, naphthalene sulfonate fumarin condensates, and the like. Among them, dialkylsulfosuccinates, alkylsulfate salts, and alkanoates are particularly preferred. The cationic interfacial activity used in the developing liquid of the present invention is particularly limited, and a conventionally known one can be used. For example, a salt, a fourth-order ammonium salt, a polyoxyethylene alkylamine salt, or a polyethylene derivative can be given. The nonionic interface used in the developing solution of the present invention is a polyethylene glycol adduct of a polyethylene glycol type, an alkyl alcohol cycloaddate, a fatty acid ethylene oxide adduct, and a poly Alcohol fatty acid ester alkane adduct, higher alkylamine ethylene oxide adduct, fatty decylamine adduct, ethylene oxide adduct of fats and oils, polypropylene glycol epoxy, dimethyl hydrazine Oxyalkylene-ethylene oxide block copolymer, dimethyl sulfonate phenoxy ether salt per acid-acidified bovine, poly-salt, phenyl phosphate phosphate butene dimer The agent has no urethramine polyamine agent, oxyethylene epoxide, ethylene ethoxide, oxirane-78- 200819915 - (propylene oxide-ethylene oxide) block copolymer, etc.; or polyol Types of fatty acid esters of glycerin, fatty acid esters of neopentyl alcohol, fatty acid esters of sorbitol and sorbitan, fatty acid esters of sucrose, alkyl ethers of polyhydric alcohols, fat oximes of alkanolamines Amines, etc. These nonionic surfactants may be used alone or in combination of two or more. In the present invention, an ethylene oxide adduct of sorbitol and/or sorbitan fatty acid ester, a polypropylene glycol ethylene oxide adduct, and a dimethyloxyxy oxide ethylene oxide block copolymer Further, a dimethyl methoxy alkane (propylene oxide-ethylene oxide) block copolymer or a fatty acid ester of a polyhydric alcohol is more preferable. Further, from the viewpoint of stable solubility to water or turbidity, the HLB (Hydrophile-Lipophile Balance) of the nonionic surfactant used in the developing liquid of the present invention is 6 The above is better, preferably 8 or more. Further, the ratio of the nonionic surfactant contained in the developing solution is preferably from 0. 01 to 10% by mass, more preferably from 0 to 5% by mass. Further, similarly, an acetylene glycol-based or acetylene-based oxyethylene adduct, a fluorine-based or a sand-based surfactant can be used. From the viewpoint of suppressing the foaming property, the surfactant used in the developing solution of the present invention is particularly preferably a nonionic surfactant. Moreover, the water-soluble polymer compound used in the developing liquid of the present invention may, for example, be a soybean polysaccharide, a modified starch, a gum arabic, a dextrin, or a cellulose derivative (for example, carboxymethylcellulose or carboxyethylcellulose). , methyl cellulose, etc.) and its modified body, pullulan, polyvinyl alcohol and its derivatives, polyvinylpyrrolidone, polypropylene decylamine and acrylamide copolymer, vinyl A-79 - 200819915 Alkyl ether/maleic anhydride copolymer, vinyl acetate/maleic anhydride copolymer, styrene/maleic anhydride copolymer, and the like. As the above-mentioned soybean polysaccharide, a well-known product can be used, and for example, various specifications of SO YAFAIB (manufactured by Fuji Oil Co., Ltd.) of a commercial product can be used. Preferably, the viscosity of the aqueous solution of 10% by mass is used in the range of 10 to 100 m P a / s e C . As the modified starch, a well-known one can be used. For example, the starch of corn, horse potato, tapioca starch, rice, wheat, or the like can be used in the range of 5 to 30 in an average of 1 molecule of glucose residues by acid or enzyme. It is produced by decomposing and adding a hydroxypropene to a base. It is also possible to use two or more kinds of water-soluble polymer compounds. The content of the water-soluble high molecular compound in the developing solution is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass. Further, the developing solution of the present invention may contain an organic solvent. Examples of the organic solvent that can be contained include aliphatic hydrocarbons (hexane, heptane, "ISOPAR-E, hydrazine, G" (made by Exxon Chemical Co., Ltd.), or gasoline, kerosene, etc.), aromatic hydrocarbons. a class (toluene, xylene, etc.), or a halogenated hydrocarbon (dichloromethane, dichloroethane, trichloroethylene, monochlorobenzene, etc.), or a polar solvent. Examples of the polar solvent 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 Benzyl ether, ethylene glycol monophenyl ether, methylphenylmethanol, n-pentanol, methylpentanol, etc.; ketones (acetone, methyl ethyl-80· 200819915 ketone, ethyl butyl ketone, Methyl isobutyl ketone, cyclohexanone, etc.; esters (ethyl acetate, propyl acetate, butyl acetate, amyl acetate, hexyl acetate, guanidine lactate, butyl lactate, butyl alcohol monobutyl) Acetate, propylene glycol monomethyl ether acetate, diethylene glycol acetate, diethyl decanoate, butyl 4-pentanone, etc.; and others (diethyl phosphate, tricresyl phosphate, N _Phenylethanolamine, N_phenyldiethanolamine, etc.). Further, when the organic solvent is not dissolved in water, it may be used in a water-soluble environment by using a boundary Φ surfactant or the like, and when the developing solution contains an organic solvent, 'from the viewpoint of safety and ignition, the solvent The concentration is preferably less than 40% by mass. The developing solution of the present invention may contain a preservative, a chelating compound, an antifoaming agent, an organic acid, an inorganic acid, an inorganic salt or the like in addition to the above. Preservatives to use phenyl alcohol or its derivatives, formalin, sulphate derivatives, sodium dehydroacetate, 4-isothiazolin-3-one derivatives, benzisothiazolin-3-one, benzotriazole Derivatives, anthracene derivatives, quaternary ammonium salts, derivatives of pyridine, φ quinoline, hydrazine, etc., di-trap, triazole derivatives, carbazole, hydrazine derivative, nitrobromo alcohol 2- Bromo-2-nitropropane-1,3 diol, 1,1-dibromo-1-nitro-2-ethanol, 1,1-dibromo-1-nitro-2-propanol or the like is preferred. The compounding compound may, for example, be ethylenediaminetetraacetic acid, a potassium salt thereof, a sodium salt thereof, diethylenetriaminepentaacetic acid, a potassium salt thereof, a sodium salt thereof, a triamethylenetetraamine hexaacetic acid, a potassium salt thereof, Its sodium salt; hydroxyethyl ethylenediamine triacetic acid, its potassium salt, its sodium salt; nitrogen triacetic acid, its sodium salt; 1-hydroxyethane-1,1-diphosphonic acid, its potassium salt, its sodium a salt; an organophosphonic acid such as an amine tris(methylenephosphonic acid), a potassium salt thereof or a sodium salt thereof, or a phosphonic acid alkane tricarboxylic acid. It is also effective to use the salt of the amine in the organic-81 - 200819915 amine instead of the sodium salt or potassium salt of the above-mentioned chelating agent. As the antifoaming agent, a compound of a conventional lanthanide-based self-emulsifying type, emulsified type, or nonionic surfactant may have a H L B of 5 or less. It is preferred to use a defoamer. Among them, any of an emulsified dispersion type and a solubilized type can be used. Examples of the organic acid include citric acid, acetic acid, oxalic acid, malonic acid, salicylic acid, octanoic acid, tartaric acid, malic acid, lactic acid, 4-pentanoic acid, p-toluenesulfonic acid, xylenesulfonic acid, phytic acid, and organic phosphonic acid. Wait. The organic acid can also be used in the form of its alkali metal or ammonium salt. Examples of the inorganic acid and inorganic salt include phosphoric acid, metaphosphoric acid, primary ammonium phosphate, ammonium diphosphate, sodium phosphate, sodium dicarbonate, potassium phosphate, potassium dimerate, sodium tripolyphosphate, potassium pyrophosphate, and six. Sodium metaphosphate, 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. As the developing liquid, it is possible to use a developing liquid developing solution as an exposed lithographic printing plate precursor, and it is preferably applied to an automatic processor to be described later. When using an automatic processor for development, the developer will gradually become weak depending on the amount of processing, and a replenishing solution or a fresh developing solution can be used to restore the processing performance. In the plate making method of the lithographic printing plate of the present invention, the supplementary mode is applicable. In the present invention, the automatic processing machine including the developing liquid supply means and the wiping member can be suitably carried out by the development processing of the aqueous solution of ρ Η 2 to 10. The automatic processing machine described in each of the publications of Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Or the automatic processing machine described in U.S. Patent No. 82-200819915 5 1 48746, the same as 5 5 6876 8 and the British Patent No. 22,977,9, which is the lithographic printing plate precursor after the image recording on the cylinder is fixed. The wiping process is performed while rotating the cylinder. Among them, an automatic processor using a rotating brush roller as a wiping member is particularly preferable. The preferred rotating brush roller which can be used in the present invention can be appropriately selected in consideration of the fact that the pixel portion is not easily injured and the toughness of the support of the lithographic printing plate precursor. The above-mentioned rotating roller brush can use a well-known thing formed by planting a brush material on a plastic or metal roller. For example, it is possible to use the material described in the Japanese Patent Publication No. 5-8-59 5 3 3 or the Japanese Patent Publication No. Hei. A metal or plastic channel material that is inserted into a brush roll that is wound on a plastic or metal roll as a core without gaps or radial. Further, the brush material can be made of a plastic fiber (for example, polyester such as polyethylene terephthalate or polybutylene terephthalate, nylon 6.6, nylon 6.1 0, polyacrylonitrile, or polyacrylonitrile. a polyacrylic acid type such as a polyalkyl (meth) acrylate or a polyolefin synthetic fiber such as a polypropylene or a polystyrene), for example, a fiber having a hair diameter of 20 to 400 μm and a hair length of 5 to 30 mm. Can be used. Further, the outer diameter of the rotating brush roller is preferably 30 to 200 mm, and the peripheral speed of the tip end of the wiping surface is preferably 0. 1 to 5 m/sec. Further, it is preferable to use a plurality of two or more rotating brush rolls. Further, with respect to the conveyance direction of the lithographic printing plate precursor of the present invention, the rotation direction of the rotary brush roller used in the present invention may be the same direction or the opposite direction, and the automatic processor shown in Fig. 12 uses two In the above rotating brush roll, 'rotate in the same direction with at least one rotating brush roller, and at least -83-200819915 1 rotating brush roller rotates in the opposite direction. Therefore, the removal of the photosensitive layer in the non-image portion is more reliable. Further, it is also effective to oscillate the rotating brush roller in the direction of the rotation axis of the brush roller. The temperature of the above developing solution can be any temperature, preferably ~50 °C. Further, in the present invention, the lithographic printing plate after the wiping treatment can be arbitrarily used, followed by water washing, drying treatment, and insensitive grease treatment. Insensitive The lipidation treatment can use well-known insensitive lipid treatment fluids. Further, the step of making the lithographic printing plate precursor to the lithographic printing plate of the present invention may be carried out by heating as necessary before exposure, during exposure, and from exposure to development. By such heating, the image formation reaction in the photosensitive layer can be promoted, and the advantage of improving the sensitivity or the printing durability or making the sensitivity stable can be produced. Further, in order to improve the image strength and the printing durability, it is also effective to perform post-heating or full-surface exposure on the image after development. Usually, the heating before development is preferably carried out under mild conditions of 150 ° C or lower. When the temperature is too high, there is a problem that even the non-image portion is whitened. The heating after development uses very strong conditions, usually in the range of 200 to 500 °C. When the temperature is too low, sufficient image enhancement cannot be obtained. When it is too high, there is a problem that the support is deteriorated and the image portion is thermally decomposed. The lithographic printing plate obtained by the above treatment is mounted on an offset printing machine, and can be used for printing a plurality of sheets. At the time of printing, in order to remove the printing plate cleaner used for the contamination on the plate, the previously used printing plate cleaner for the PS plate can be used, and -84-200819915, for example, CL-1, CL-2, CP, CN can be used. -4, CN, CG-1, PC-1, SR, 1C (made by Fuji Photo Film Co., Ltd.). [Examples] Hereinafter, the present invention will be described by way of Examples, but the present invention is not limited thereto. [Manufacturing of Support] In order to remove the rolling oil on the surface of an aluminum plate (material 1 0.05) having a thickness of 0.3 mm, a 1% by mass aqueous solution of sodium aluminate was used, and after degreasing treatment at 50 ° C for 30 seconds, Use 3 bundles of nylon brushes with a diameter of 3 mm, and a pumice-water suspension with a diameter of 25 μm (compared to 1.1 g/cm 3 ), brush the aluminum surface to a rough surface, and use water. Wash thoroughly. The plate was immersed in a 25 mass% nitric acid aqueous solution at 45 °C for 9 seconds, and after rinsing, it was further immersed in a 20 mass% nitric acid aqueous solution at 65 °C for 20 seconds and washed with water. At this time, the etching amount of the rough surface was about 3 g/m 2 . Then, electrochemical roughening treatment was continuously performed using an alternating voltage of 60 Hz. The electrolytic solution at this time was 1% by mass of nitric acid, water-soluble, liquid (containing 0.5 mass%/〇 aluminum ion), and the liquid temperature was 50 °C. The AC power waveform was subjected to electrochemical graining treatment using a current 値 from zero to a peak TP of 0.8 msec, a duty ratio of 1:1, a trapezoidal rectangular wave, and a carbon electrode as a counter electrode. The auxiliary anode is made of ferrite iron. The current density is 30 A/dm2 at the peak of the current, and the auxiliary anode is shunted by 5% of the current flowing through the power supply. In the case of nitric acid electrolysis, the amount of electricity is 175 C/dm2 when the aluminum plate is an anode. Thereafter, it was washed with water by spraying. Next, using an aqueous solution of 〇5·5 °/〇 (containing 0.5% by mass of aluminum-85-200819915) and an electrolyte having a liquid temperature of 50 °C, the amount of electricity when the nameplate is the anode is 5 OC/dm2. Under the conditions, electrochemical roughening treatment was carried out by the same method as nitric acid electrolysis, followed by washing with water. To the plate, a 15 mass% aqueous sulfuric acid solution (containing 0.5 mass% of aluminum ion) was used as an electrolytic solution, and a DC anodic oxide film of 2.5 g/m 2 was placed at a current density of 15 A / d m 2 , and then washed with water and dried. The center line average roughness (Ra) of the obtained support was measured using a needle having a diameter of 2 μm to be 0.51 μm. Further, after the bar was applied with the following primer liquid, it was dried in an oven at 80 ° C for 1 〇 second, and dried at a coating amount of 10 mg / m 2 to prepare a support having an undercoat layer. <Bottom coating liquid> • The following primer compound (1) 0.017 g

• Water 1 · 〇 0 g [Examples 1 to 15 and Comparative Examples 1 to 4] [Production of lithographic printing plates (1) to (15) and comparative lithographic printing plates (1) to (4)] On the support of the undercoat layer, the bar is coated with the photosensitive layer coating liquid (1) of the following composition, and then dried in an oven at 70 ° C for 60 seconds to form a dry coating -86-200819915. The amount of cloth is 1.1 gram. a photosensitive layer of a square meter of a photosensitive layer coating liquid (1) composed of the following composition was applied to the photosensitive layer having a dry coating amount of 0.75 g/m 2 , and dried at 125 ° C for 70 seconds. The lithographic printing plate precursor (1) of Example 1 was produced. Similarly, the lithographic printing plates (2) to (15) of Comparative Examples 2 to 15 and Comparative Examples 1 to 4 and the comparative lithographic printing plates (1) to (4) were produced. <Photosensitive layer coating liquid (1): alkali-soluble binder system> (Initiation system is described in Table-1)

• Initiator 〇. 2g • Sensitized pigment 〇. 1g • Total sensitizer 〇. 3g (polymerization) • Adhesive polymer (described in Table-1) 3 · 0g • Polymeric compound 6.2克-trimer isocyanate Ο modified diacrylate (ARONIX M-215 made by East Asia Synthetic Co., Ltd.) • Colorless crystal violet 0.2 g • The following fluorine-based surfactant (1) 〇·1 g 000〇2" 4. 6 households 13 C one one (〇. 3~) 22 - -〇H 0 Fluoride surfactant (1) • The following microcapsule dispersion 25.0 g • Methyl ethyl ketone 3 5 · 0 g • 1 -Methoxy-2-propanol 35·0 g-87- 200819915 (Preparation of microcapsule dispersion) 1 g of trimethylolpropane and xylene diisocyanate adduct of oil phase component (Mitsui Takeda Chemical Co., Ltd. (Stock), TAKENATE D·11 0N), 4.15 g of trimeric isocyanate EO modified diacrylate (ARONIX M-215 made by East Asia Synthetic Co., Ltd.), and 0.1 g of PAIONIN A-41C (Bamboo Oil (manufactured by the company), dissolved in 17 g of ethyl acetate. A 4% by mass 7jc solution of PVA-205 having a water content of 4 grams was prepared. The oil phase component and the water phase component were mixed, and then emulsified at 1 200 rpm for 10 minutes using a homogenizer. The obtained emulsion was added to 25 g of distilled water, and then stirred at room temperature for 30 minutes, and then stirred at 40 ° C for 3 hours. The microcapsule liquid thus obtained was diluted with distilled water to have a solid content concentration of 20% by mass to obtain a microcapsule dispersion. The average particle size is 0.25 microns. <Protective layer coating liquid (1)> • The following mica dispersion 1 3.0 g • Polyvinyl alcohol (saponification degree 98 mol%, polymerization degree 500) 1·3 g• 2-ethylhexylsulfonate Sodium succinate 0.2 g • Poly(vinylpyrrolidone/vinyl acetate (1/1)) Molecular weight 70,000 g • Surfactant (E ma 1 e X 7 1 0, Japan (made by EMULSION) 0 ·05 g • Water 1 3 3 g (Preparation of mica dispersion) Add 32 g of synthetic mica in 3 68 g of water (“SOMASIF ME-1 00”: CO-OP CHEMICAL company, aspect ratio: 10〇〇 or more ), -88- 200819915 Then, using a homogenizer to disperse to an average particle diameter (laser scattering method) of 0.5 μm, a mica dispersion was obtained. [Examples 16 to 30 and Comparative Examples 5 to 8] [Production of lithography] Printed version of the original (16) ~ (30) and comparative lithographic printing original (5) - (8)]

A printing plate precursor (16) to (30) is produced in the same manner as the lithographic printing plate precursor (1) except that the photosensitive layer coating liquid (1) is changed to the photosensitive layer coating liquid (2) having the following composition. And compare lithographic printing original (5) ~ (8). <Photosensitive layer coating liquid (2): Hydrophobic binder system> (Initiation system: described in Table-2) • Initiator 0.2 g • Sensitized colorant 1. 1 g • Total sensitizer 〇. 3 g (Polymerization) • Adhesive polymer (described in Table-2) 3.0 g • Polymeric compound 6.2 g of trimeric isocyanate E 0 modified diacrylate (ARONIX M-215 manufactured by Toagosei Co., Ltd.) • Colorless Crystal Violet · 2 g • The following fluorine-based surfactant (1) 〇·1 g

One OH 25.0 g of fluorine-based surfactant (1) • The following microcapsule dispersion-89-200819915 • Methyl ethyl ketone 35.0 g • 1-methoxy-2-propanol 35.0 g [lithographic original version of Evaluation] Using lithographic printing plates (1) to (30) and comparative lithographic printing plates (1) to (8), exposure, development, and evaluation of sensitivity, development, and storage stability were carried out as follows. (Sensitivity evaluation) The Fuji STEP GUIDE (△ D = 0·15 5 and the transmitted light density discontinuously changed. The gray scale) of Fuji Photo Film Co., Ltd. is adhered to the original of the lithographic printing plate, and the xenon lamp is used as the light source. For the purpose of estimating the exposure suitability for short-wave semiconductor lasers, KENKO-BP-40 was used as a filter, and exposure light was applied at a prescribed exposure energy using a monochromatic light of 400 nm. The exposed lithographic printing plate precursor was subjected to development processing by an automatic developing processor using a developing liquid having the following composition. The automatic developing processor has two rotating brush rollers, and the first rotating brush roller that the lithographic printing plate original first contacts is a fiber made of polybutylene terephthalate (the hair diameter is 200 μm, and the hair length is 17 mm) outer diameter 90 mm brush roller, in the same direction as the conveying direction, so that it is 200 rpm (the front end speed of the brush is 0.94 m / s), the second rotating brush roller is implanted A brush roller having an outer diameter of 60 mm (fiber diameter of 200 μm and hair length of 17 mm) having a diameter of 200 μm and a hair length of 17 mm is 200 rpm per minute in the opposite direction to the conveying direction (brush) The previous peripheral speed is 0.63 meters / sec). The original speed of the lithographic printing plate is 100 cm/min. The developing liquid is supplied to the plate by the circulation pump by a circulation pump and is supplied to the plate -90-200819915. The tank capacity of the developing solution is 10 liters. (Photographic liquids used in Examples 1 to 15 and Comparative Examples 1 to 4) ρ Η 1 1 . 9 5 composed of the following composition: water-soluble liquid · sodium hydroxide 〇 · 2 g • 1 Κ Potassium citrate 2 · 4 g (SiO 2 / K 20 = l , 9) • The following compounds (1) 5 · 0 g • Ethylenediaminetetraacetic acid · 4N a salt 〇 · 1 g • Water 91.3 g (in the examples The imaging solution used in 16~30 and Comparative Examples 5~8 (pH: about • water 100 g • benzyl alcohol 1 g • polyoxyethylene naphthyl ether 1 g (oxygen extension. ethyl average n=l3) • Dioctyl sulfosuccinate sodium salt 0.5 g • Gum arabic 1 g • Ethylene glycol 0.5 g • First generation ammonium phosphate 0.05 g • Citric acid 0,05 g • Ethylene diamine tetraacetate 4 sodium Salt 0 · 0 5 g In the obtained lithographic printing plate, read the maximum number of segments of -91-200819915 of the gray scale that has completely removed the image, and obtain the exposure energy from the calculated transparency sensitivity (mj/cm 2 ) When the exposure amount was small, it was evaluated as high sensitivity. The results are shown in Table 1. (Development evaluation) For the lithographic printing plate precursor, the exposure apparatus used Violet manufactured by FUJIFILM Electronic Imaging Ltd. Conductor laser regulator Vx9600 (InGaN semiconductor laser 405 nm ± 1 〇 nanometer light / output power 30 mW), with an exposure of 90 / / J / cm ^ 2, resolution 2438dpi, φ by Fuji Photo Film FM SCREEN TAFFETA20 To draw a 35% flat net. Then, in the same manner as the above-mentioned sensitivity evaluation imaging step, after the lithographic printing plate original image is processed to a degree of about 100 square meters, the visual initiator component is directed to the automatic developing processor. The evaluation was carried out, and it was judged that it was X, it was difficult to judge △, and no precipitation was 〇. The results are shown in Table 1. (Evaluation of preservation stability) For the lithographic printing plate original, immediately after manufacture (condition i), and After storage at 60 ° C for 1 day under forced conditions (condition ii), exposure and development were performed in the same manner as the sensitivity evaluation described above to obtain the respective transparency sensitivity. The transparency sensitivity and condition of condition i were obtained. The difference in transparency sensitivity of ii is defined as the transparency sensitivity ratio (condition ii/condition i). The closer the 値 is to 1, the lithographic printing plate original and the forced lithographic original plate are formed in the image. Min The change in degree is small, and it can be said that the storage stability is high. Further, the amount of the initiator dissolved in an aqueous solution of pH 1 1.95 is determined as follows. A specific amount of the initiator is dissolved in 2 ml of methyl ethyl group. In the ketone, 98 ml of an aqueous solution of ρ Η 1 1 . 9 5 was added thereto. After stirring for 1 hour - 92 - 200819915, it was filtered using a microfilter. After further diluting the filtrate by a factor of 5, UV measurement was carried out by a usual method. The amount of dissolution was calculated from the absorption intensity, and converted into an amount of dissolution per 1 liter of the aqueous solution of pH 11.95. The results are shown in Table 1. Further, the amount of the initiator dissolved in an aqueous solution of pH 4.5 was measured as follows. A specific amount of the initiator was dissolved in 2 ml of methyl ethyl ketone, and 98 ml of an aqueous solution which had been prepared to have a pH of 4.5 at 25 ° C was added thereto. After stirring for 1 hour, it was filtered using a microfilter. The filtrate was further diluted 5 times, and UV measurement was carried out by a usual method. The amount of dissolution was calculated from the absorption intensity, and converted into an amount of dissolution per 1 liter of the aqueous solution of p Η 4.5. The results are shown in Table 2.

•93- 200819915 Table-1 Initiation Evaluation Results Sensitized Colorant (g) Initiator (g) Co-sensitizer (g) Adhesive Polymer (g) Compound Solubility (mg/L) in the Developer Gas precipitation transparency sensitivity (mJ/cm 2 ) Transparent sensitivity ratio Example 1 Hl (10) 1-3 (0.90) R-K0.20) Ρ-6 (3,5 g) 450 〇0.32 1.04 Example 2 Hl(lO) 1-4(1.2) R-K0.20) Ρ·6 (3.5 g) 470 〇0.28 1.04 Example 3 Hl(lO) 1-12(1.3) R-K0.20) Ρ-6( 3·5 克 490 〇0.29 1.02 Example 4 Hl(lO) 1-16(1.25) R-K0.20) Ρ-6(3·5 g) 1200 〇0.45 1.02 Example 5 Hl(lO) 1- 17(0.9) Rl(0.20) Ρ-6(3.5 g) 450 〇0.41 1.2 Example 6 Hl(lO) 1-18(1.2) R-K0.20) Ρ-6(3·5 g) 850 〇0.35 1.25 Example 7 Hl(lO) 1-24(1.1) R-K0.20) Ρ-6(3·5 g) 660 〇0.46 1.09 Example 8 Hl(lO) 14(0.91) R-K0.20) Ρ-6 (3.5 g) 420 〇0.28 1.02 Example 9 Hl(lO) 1-6(0.90) R-K0.20) Ρ-6(3·5 g) 390 〇0.27 1 Example 10 Hl(lO) 1-21 (0.90) Rl (0.20) Ρ-6 (3.5 g) 450 〇0.35 1.06 Example 11 H -l(lO) 1-22(0.90) R-K0.20) Ρ-6(3.5 g) 430 〇0.38 1.02 Example 12 Hl(lO) 1-7(0.85) R-K0.20) Ρ-6 (3.5 g) 300 〇0.29 1.01 Example 13 Hl(lO) 1-8(0.95) R-K0.20) Ρ·6(3·5 g) 350 〇0.32 1.05 Example 14 Hl(lO) 1-5 (0.91) R-K0.20) Ρ-6 (3.5 g) 320 〇042 1.15 Example 15 - Comparative Example 1 Hl(lO) Hl(lO) 1-9(1.02) Rl(0.20) Ρ-6(3.5 %) 300 〇0.44 1.36 T-K0.90) Rl(0.20) Ρ·6(3·5 克) 10 X 0.28 1.05 Comparative Example 2 Hl(lO) T-2(0.90) R-K0.20) Ρ- 6 (3.5 g) 30 X 0.29 1,05 Comparative Example 3 Hl(lO) T-3(0.90) Rl(0.20) Ρ-6(3·5 g) 20 X 0.32 1.09 Comparative Example 4 Hl(lO) Τ- 4(0·91) Rl(0.20) Ρ-6(3·5 grams) 5 X 0.35 1.15

• From Table 1, it is found that the initiator used in the present invention exhibits an overwhelming high alkali solubility when compared with the compound of the comparative example, and does not generate a developing gas component. Further, from Examples 1 and 2, it was found that the alkali developing solution can have high sensitivity by protecting the substituent of the hydroxyl group. Further, when Example 8 is compared with Examples 12 to 15, it is found that a substituent of a phenyl group which is bonded to a carbon atom (present between N-N) is preferably a chlorine atom, and a substitution position is preferably an ortho position. -94- 200819915 Table-2 Initiation evaluation results of binder compounds in the imaging-sensitized sensitized coloring agent initiator sensitizer polymer solubility machine gas transparency sensitivity ratio (g) (g) (g) (g) (mg/L) Precipitation (mJ/cm 2 ) Example 16 H-K1.0) 1-3 (0.90) R4 (0.20) Ρ-1 (3·5 g) 450 〇0.31 1.02 Example 17 Hl(lO) 1-4(1.2) R-K0.20) Ρ-3 (3·5 g) 190 △ 0.3 1.03 Example 18 Hl(lO) 1-12(1.3) R-K0.20) Ρ- 2 (3.5 g) 180 △ 0.3 u Example 19 H-K1.0) 146 (1.25) R-K0.20) Ρ_5 (3.5 g) 1000 〇0.42 1.06 Example 20 H-K1.0) 147 (0.9) Rl (0.20) Ρ·2 (3·5 g) 420 〇0.41 1.2 Example 21 Hl(lO) 1-18(1.2) R-K0.20) Ρ-4(3·5 g) 750 〇0.33 1.3 Implementation Example 22 Hl(lO) 1-24(1.1) R-K0.20) Ρ-4 (3.5 g) 200 Δ 0.45 1.15 Example 23 H-K1.0) 1-1 (0.91) R-K0.20) Ρ-Κ3.5 克Γ 190 Δ0.3 1.02 Example 24 H-K1.0) 1-6 (0.90 R-1 (0,20) Ρ4 (3.5 g) 180 △ 0.31 1 Example 25 Hl(lO) 1 -21(0.90) R-K0.20) Ρ-3 (3.5 grams) 210 △ 0.45 1.08 Example 26 Hl(lO) 1-22(0.90) R-K0.20) Ρ-3 (3.5 g) 220 Δ 0.46 1.06 Example 27 Hl(lO) 1-7(0.85) R-K0.20) Ρ- Κ3.5 g) 190 Δ 0.34 1.02 Example 28 Hl(lO) 1-8(0.95) R-K0.20) Ρ-Κ3.5 g) 180 △ 0.36 10.7 Example 29 Hl(lO) 1-5( 0.91) Rl (0.20) Ρ-Κ3.5 g) 200 Δ 0.42 1.2 Example 30 Hl(lO) 1-9(1.02) R-K0.20) P-K3.5 g) 220 △ 0.45 1.4 Comparative Example 5 Hl(lO) T-K0.90) R-K0.20) Ρ-3(3·5 g) 10 X 0.30 1.2 Comparative Example 6 Hl(lO) Τ·2(0.90) R-K0.20) Ρ- 3 (3·5 g) 30 X 0.31 1.4 Comparative Example 7 Hl(lO) T-3(0.90) R-K0.20) Ρ-3 (3.5 g) 20 X 0.33 1.3 Comparative Example 8 Hl(lO) Τ- 4(0.91) Rl(0.20) Ρ-3(3.5 g) 5 X 0.38 1.3

From Table 2, it was found that the initiator used in the present invention showed high solubility in a weak acid aqueous solution and was less likely to generate a developing gas component when compared with the compound of the comparative example. In addition, the biggest difference from the alkali image development, because the aqueous solution is weakly acidic, it is impossible to hydrolyze the lanthanide functional group, and the hydroxy group is used to protect the hydroxy group (Examples 16.6, 17 and so on) When the image is not produced at all, it is possible to confirm that a certain amount of gas will be generated. This is also the same in the carboxylic acid ester-based compound (it is estimated that S is not hydrolyzable and becomes a gas component). Even in this case, the solubility of -95-200819915 is improved as compared with the comparative example, and it is possible to give a good overall result. From this, it was found that when weak acid development is performed, the substituent imparted to the compound has a hydroxyl group as a hydrazine. The initiator of the present invention used in the initiators of Tables 1 and 2 is any of the compounds exemplified above. Further, the structures of the sensitizing toner Η-1, the initiators T-1 to T-4, the co-sensitizer R-1, and the binder polymers P] to P-5 are as follows. Further, the following initiators T-1 to T-4 used in the comparative examples are compounds outside the range of the initiator used in the present invention.

<Hydrophobic binder polymer> -1,? -2,? -3,? The weight average molecular weight of -4 is 80,000, 70,000, 1,000,000, and 90,000, respectively. -96- 200819915

Further, the acid value of Ρ-1 to ρ·4 is 0.3 meq/g or less.

Acid value 2.0 6 meg / g <alkali-soluble binder polymer> P-6: allyl methacrylate/methacrylic acid/N-isopropylacrylamide copolymer (copolymerized molar ratio 67/ 1 3 /20) [Simple description of the diagram] 〇y\,, [Description of main component symbols] Μ . \\ -97-

Claims (1)

200819915 X. Patent application scope: 1. A photosensitive composition comprising: (A) a dimethicone compound having the structure represented by the following formula (I), (B) having an absorption at 350 nm to 850 nm The maximum wavelength is (7) "the sensitizing colorant, and (C) the polymerizable compound, (In the formula (I), Ri to R6 represent any one of an aryl group which may have a substituent and a heteroaryl group which may have a substituent, and at least two of Ri to R6 have a COOR7 group, a S03R8 group. The aryl or heteroaryl group of the substituent of the group, the P03R9 group, the OH group, and the 〇C〇Rl° group, and the R7~Ri〇 each independently represents a valence group of a non-hydrogen atom). 2. The photosensitive composition of claim 1, wherein the sensitizing colorant (B) is selected from the group consisting of a coumarin coloring material, a styrene based coloring material, an anthocyanin coloring material, and a merocyanine coloring material. An image recording material which is provided on a support and which has a photosensitive layer containing a photosensitive composition according to claim 1 or 2. 4 · An image recording method using a laser light source having a wavelength shorter than 45 〇 nanometers for an image recording material having a photosensitive layer containing a photosensitive composition of the first or second photosensitive composition of the patent application scope on the support Scanned to expose -98- 200819915 light. A lithographic printing plate on a support having a photosensitive layer containing the photosensitive composition of the first or second aspect of the patent application. 6. A method for producing a lithographic printing plate, comprising the steps of: exposing a lithographic printing plate precursor having a support, a photosensitive layer, and a protective layer in the following order at a laser wavelength of 350 to 4 50 nm; Thereafter, the photosensitive layer of the protective layer and the non-exposed portion is removed in the presence of a developing solution having a pH of 10 to 14; wherein the photosensitive layer contains (A) a second microphone having a structure represented by the following formula (I) a compound of the type (B) having a sensitizing color absorbing maximum wavelength λ max at 350 nm to 850 nm, (C) a polymerizable compound, and a (D-I) alkali-soluble binder polymer, (In the formula (I), Ri to R6 represent any one of an aryl group which may have a substituent and a heteroaryl group which may have a substituent, and at least two of Ri to R6 have a selected from the group consisting of COOR7 group and S03R8. An aryl or heteroaryl group of a substituent of a P03R9 group, an OH group, and an OCORio group, and R7 to Rm each independently represent a valence group of a non-hydrogen atom). 7 - A method for producing a lithographic printing plate, comprising the steps of: lithographic printing plate precursor having a support, a photosensitive layer, and a protective layer in the following order, after exposure to a laser having a wavelength of 350 to 450 nm The photosensitive layer -99-200819915 layer of the protective layer and the non-exposed portion is removed in the presence of a developing solution having a pH of 2 to 10; wherein the photosensitive layer contains (A) one of the structures of the following formula (1): The compound and (B) have a sensitizing colorant having a maximum absorption wavelength λ max of from 350 nm to 850 nm, a polymerizable compound, and an acid value of (D-2) of 0.3 meq / g or less. Hydrophobic binder polymer (In the formula (I), Ri to L are each one of an aryl group which may have a substituent and a heteroaryl group which may have a substituent, and at least two of them have a group derived from a COOR7 group, a S03R8 group, and a P03R9 group. The group, the 0H group, and the 0COR1 (the aryl or heteroaryl group of the substituent, the R7 to RlG each independently represent an atomic group of one of the hydrogen atoms). -100- 200819915 VII. Designation of the representative representative: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: Μ 〇 j\\\ 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: