WO2008026465A1 - Photosensitive lithographic printing plate material - Google Patents

Abstract

A lithographic printing plate material that is suitable for exposure with laser beams of 350 to 450 nm emission wavelength and used in a printing plate production process through exposure, heat treatment and plate making, and that while maintaining high sensitivity and plate life, is less in the change of halftone dot reproduction over time from exposure to heat treatment. Accordingly, there is provided a photosensitive lithographic printing plate material including a photosensitive layer containing a polymerizable ethylenic unsaturated bond-containing compound, a polymerization initiator, a spectral sensitizer and a polymer binder, characterized in that the photosensitive layer contains a monofunctional monomer of 2.3 to 6.0 D dipole moment as the polymerizable ethylenic unsaturated bond-containing compound.

Description

 Specification

 Photosensitive lithographic printing plate material

 Technical field

 [0001] The present invention relates to a photosensitive lithographic printing plate used in a so-called computer “to-plate” (hereinafter referred to as “CTP” <^ ”) system. The present invention relates to a photosensitive lithographic printing plate material suitable for exposure with a 450 nm laser beam. Background art

 [0002] In recent years, digital technology for processing, storing, and outputting image information electronically using a computer has become widespread, and digital image information has been used in the preparation of printing plates for offset printing. Therefore, a so-called CTP system that scans highly directional laser light and records directly on a photosensitive lithographic printing plate has been developed and is in practical use.

 Of these, in the field of printing that requires a relatively high printing durability, a printing plate material having a negative photosensitive layer having an image recording layer containing a polymerizable compound on an aluminum support is provided. It is known to use.

 [0004] A photosensitive lithographic printing plate for CTP that records digital data with a laser contains, for example, titanocene, a polymerization initiator described in JP-A-9-80750 and JP-A-10-101719, and a specific dye. Those having a photopolymerizable photosensitive layer are known! However, since these photosensitive lithographic printing plates use a relatively long wavelength visible light source as a light source, it is necessary to carry out plate making work for making a printing plate under a safe light of a dark red light. There was a demand for being able to handle under a brighter yellow light than the bad (lighting room)

Yes

 [0005] And, a high-power and small-sized blue-violet laser with a wavelength of 390 to 430 nm can be easily obtained, and the development of a photosensitive lithographic printing plate suitable for this laser wavelength will make it possible to increase the light room. It has been.

On the other hand, as a plate making method of a printing plate material having a negative photosensitive layer having an image recording layer containing a polymerizable compound, in order to improve sensitivity, printing durability, etc., heat treatment is performed after image exposure. Is known, and then development processing is known (see Patent Documents 1 and 2). [0007] However, in the method of performing the plate-making process by performing post-exposure heat treatment! /, It is high! /, A force that is a preferred plate-making method in terms of obtaining printing durability, in conventional lithographic printing plate materials, There were problems such as sensitivity and printing durability being still insufficient, and large fluctuations in halftone dot reproducibility over time from exposure to heat treatment.

 Patent Document 1: Japanese Patent Laid-Open No. 2001_175006

 Patent Document 2: Japanese Translation of Special Publication 2002-537419

 Disclosure of the invention

 Problems to be solved by the invention

[0008] The present invention has been made in view of the above problems, and a problem to be solved is a lithographic printing plate material used in a plate making method in which a post-exposure heat treatment is carried out for plate making, and has high sensitivity and resistance An object of the present invention is to provide a lithographic printing plate material with little fluctuation of halftone dot reproducibility over time from exposure to heat treatment while maintaining a printing press.

 Means for solving the problem

[0009] The above-mentioned problem according to the present invention is solved by the following means.

 1. A photosensitive lithographic printing plate material having a photosensitive layer containing a polymerizable ethylenically unsaturated bond-containing compound, a polymerization initiator, a spectral sensitizer, and a polymer binder on a support. The photosensitive lithographic printing plate material is characterized in that the photosensitive layer contains a monofunctional monomer having a dipole moment of 2.3 to 6.0 D as a polymerizable ethylenically unsaturated bond-containing compound. .

 [0011] 2. The photosensitive lithographic printing plate material as described in 1 above, wherein the monofunctional monomer is an acrylamide derivative.

[0012] 3. The photosensitive lithographic printing plate material as described in 2 above, wherein the acrylamide derivative is ア ル キ ル -alkylacrylamide.

[0013] 4. The photosensitive layer described above, wherein the photosensitive layer contains, as a polymerizable ethylenically unsaturated bond-containing compound, a polyfunctional acrylate having an amide bond and a tertiary amino group in one molecule. The photosensitive lithographic printing plate material according to any one of -3.

The invention's effect [0014] A lithographic printing plate material suitable for exposure with a laser beam having an emission wavelength in the range of 350 to 450 nm by the above means of the present invention and used in a plate making method in which post-exposure heat treatment is performed. Thus, it is possible to provide a lithographic printing plate material with little fluctuation in halftone dot reproducibility over time from exposure to heat treatment while maintaining high sensitivity and printing durability.

 BEST MODE FOR CARRYING OUT THE INVENTION

 The photosensitive lithographic printing plate material of the present invention comprises a photosensitive layer containing a polymerizable ethylenically unsaturated bond-containing compound, a polymerization initiator, a spectral sensitizer, and a polymer binder on a support. In the photosensitive lithographic printing plate material provided, the photosensitive layer contains a monofunctional monomer having a dipole moment of 2.3 to 6.0 D as a polymerizable ethylenically unsaturated bond-containing compound. Features. Thereby, it is possible to provide a photosensitive lithographic printing plate material having high sensitivity and high printing durability and excellent stability after exposure.

 [0016] Hereinafter, the present invention, components, and the like will be described in detail.

 [0017] (Polymerizable ethylenically unsaturated bond-containing compound)

 The polymerizable ethylenically unsaturated bond-containing compound is a compound that can be polymerized by a reaction with a product resulting from a reaction of a polymerization initiator by image exposure, and is preferably a monomer (monomer). That is, dimers, trimers, etc., and oligomers can also be used. As the polymerizable ethylenically unsaturated bond-containing compound according to the present invention, a reaction with a radical species generated from the polymerization initiator according to the present invention is possible. As a trigger, a wide range of compounds that can initiate the polymerization reaction can be used.

 [0018] However, the photosensitive layer of the photosensitive lithographic printing plate material of the present invention contains a monofunctional monomer having a dipole moment of 2.3 to 6. OD as a polymerizable ethylenically unsaturated bond-containing compound. It is necessary to do.

 Here, “monofunctional” means that there is one polymerizable ethylenically unsaturated bond.

In addition, “dipole moment” is an electric dipole defined in various books and literatures represented by a dictionary of physics and chemistry (published by Iwanami Shoten, for example, page 751 of the 3rd edition supplement published in 1987). In the present invention, the whole monofunctional monomer molecule is represented by a vector sum of each bond moment. Note that the dipole moment according to the present invention is the whole molecule. It is the sum of the absolute values of the field vector quantities.

 [0020] The method of obtaining the dipole moment can be calculated using, for example, commercially available calculation software. In the present invention, calculation was performed using Fujitsu Win MOPAC 3.0. The polymerizable ethylenically unsaturated bond-containing compound used in the present invention is preferably a monofunctional monomer having a dipole moment in the range of 2.3 to 6. OD 2.5 to 5.5D is more preferable. I like it. That is, the monofunctional monomer according to the present invention can include the following exemplified compounds and the like. When these are calculated and calculated with the above software, the dipole moment falls within the above range, and therefore, the monofunctional monomer within the range. However, it can be said that it is useful in achieving the object of the present invention and producing the effects of the invention. Regarding the error of the result due to the setting condition in the above calculation, it is useful as the monofunctional monomer according to the present invention if it is within the above range in consideration of rounding off the second decimal place.

 [0021] It is presumed that the monofunctional monomer according to the present invention exerts the effects of the present invention by being in the above-mentioned dipole moment range because the radical activity is high and the reactivity is high in the above-mentioned range. The

 <Monofunctional monomer>

 Examples of the monofunctional monomer according to the present invention include acrylamide derivatives, acrylonitrile derivatives, (meth) acrylic acid derivatives, and the like, and acrylamide derivatives are particularly preferable. For example, acrylamide, methacrylolamide, N-methylacrylamide, dimethylacrylamide, alitaroylmorpholine, N-isopropylacrylamide, N-tert-butylacrylamide, N-phenylacrylamide, diacetone acrylamide, atalyloylbiperidine, gel Examples include til acrylamide, 2-hydroxyacrylamide, and dimethylaminopropyl acrylamide. Of these, N-alkylacrylamides such as N-methylacrylamide, N-isopropyl attalinoleamide, N-tert-butylacrylamide and the like are particularly preferable.

 [0022] The addition amount is preferably from 0.3 to 20 parts by mass of the solid content of the photosensitive layer, more preferably from 0.3 to 15 parts by mass.

[0023] In addition to the polymerizable ethylenically unsaturated bond-containing compound, the photosensitive layer according to the present invention is generally used for general radical polymerizable monomers and ultraviolet curable resins. Polyfunctional monomers having a plurality of addition-polymerizable ethylenic double bonds in the molecule or polyfunctional oligomers can be used. The compound is not limited, but in the present invention, it is also preferable to contain a polymerizable ethylenically unsaturated bond-containing compound having a photooxidizable group in the molecule as the polymerizable ethylenically unsaturated bond-containing compound. Good.

 [0024] Examples of the photooxidizable group include a thio group, a thioether group, a ureido group, an amino group, and an ethanol group. Specific examples of these groups include triethanolamine group, triphenylamine group, thiolide group, imidazolyl group, oxazolyl group, thiazolyl group, acetylethylacetonyl residue, N-phenyldaricin residue and ascorbic acid residue. The ability to raise S Particularly preferred among these are secondary or tertiary amino groups.

 A preferred embodiment of the present invention is a polymerizable ethylenically unsaturated bond-containing compound having an amide bond and a secondary or tertiary amino group in the molecule as the polymerizable ethylenically unsaturated bond-containing compound. It is to contain. In particular, polyfunctional acrylate compounds having an amide bond and a tertiary amino group in the molecule are preferred.

 [0026] Since the polymerizable ethylenically unsaturated bond-containing compound preferably used in the present invention has an amide bond, it is a tough and highly adhesive cured film due to the action of the dispersion force and intermolecular force of the amide bond. Can be formed. At the same time, by having a secondary or tertiary amino group, the photo-oxidation action of the group can improve the crosslinking density at the time of curing, and a dense and strong cured film can be formed. .

 Examples of the photooxidizable group having such an action include a thio group, a thioether group, a ureido group, an amino group, and an enol group. Specific examples of these groups include triethanolamine group, triphenylamine group, thiolide group, imidazolyl group, oxazolyl group, thiazolyl group, acetylethylacetonyl residue, N-phenylglycine residue and Ascorbic acid residues can be mentioned. Of these, particularly preferred are secondary or tertiary amino groups.

[0028] Specific examples of the compound containing a photooxidizable group are described in European Patent Application Publication Nos. 287, 818, 353, 389 and 364, 735. Preferred among the compounds described therein are tertiary amino groups or ureido groups and urethanes. The compound which has group can be mentioned.

[0029] As compounds having at least one photooxidizable group and at least one urethane group, JP-A 63-260909, JP 2669849, JP-A 6-35189, JP The thing of 2001-125255 can also be mentioned.

[0030] A polymerizable ethylenically unsaturated bond-containing compound having an amide bond and a secondary or tertiary amino group in the molecule as a preferred embodiment will be described in detail.

[0031] The polymerizable ethylenically unsaturated bond-containing compound having an amide bond and a secondary or tertiary amino group in the molecule according to the present invention has a solubility in pure water at 25 ° C of 1% by mass. More power to dissolve S preferred. More preferably, it is 3 mass% or more, More preferably, it is 5 mass% or more, Most preferably, it is 10 mass% or more.

[0032] The compound having such characteristics includes (a) a polyhydric alcohol containing a secondary or tertiary amino group in the molecule, (b) a polyvalent isocyanate compound, and (c) a hydroxyl group in the molecule. It can be obtained as a reaction product of a compound containing an ethylenic double bond capable of addition polymerization.

 [0033] More preferably, further (d) introducing an amino group-free polyhydric alcohol unit such as glycols, suppressing the mol ratio of the compound having a double bond to less than 40%, More preferably it is less than 30%, particularly preferably less than 25%.

 [0034] Details of components of a polymerizable ethylenically unsaturated bond-containing compound having an amide bond and a secondary or tertiary amino group in the molecule

 [(A) Polyhydric alcohol containing secondary or tertiary amino groups]

The polyhydric alcohols containing secondary or tertiary amino groups in the molecule include triethanolamine, N-methylethanolamine, N-ethyljetanolamine, Nn-butyljetanolamine. , N-tert.-Butyljetanolamine, N, N Di (hydroxyethynole) aniline, N, N,, ', 一, One-tetrahydroxy-2-hydroxypropylethylenediamine, ρ Toryljetanolamine, Ν , Ν, Ν ', Ν, 1-tetraethyl 2-hydroxyethylenethylenediamine, Ν, Ν-bis (2-hydroxypropinole) aniline, allyljetanolamine, 3 (dimethylamino) 1, 2 propanediol, 3 jetylamino 1, 2 Propanediol, Ν, Ν Di (η-propyl) amino-2, 3 Propanediol, Ν , N Di (isopropinole) amino-2,3 propanediol, 3- (N-methyl-Nbenzylamino) 1,2-propanediol, and the like.

 [(B) Polyvalent isocyanate compound]

 The polyvalent isocyanate compound that can be used in the present invention means an organic compound having two or more isocyanate groups in the molecule. Therefore, it may be a multimer such as a polyol adduct of polyvalent isocyanate, a biuret or an isocyanurate.

 [0036] Diisocyanate compounds include butane 1,4-diisocyanate, hexane 1,6-diisocyanate, 2 methinorepentane 1,5 diisocyanate, octane 1,8-diisocyanate, 1,3-diisocyanate methyl Norecyclohexanone, 2, 2, 4-trimethylenohexane 1,6-diisocyanate, isophorone diisocyanate, 1,2-phenolic diisocyanate, 1,3-phenylene diisocyanate, 1, 4-phenylene diisocyanate, tolylene 2,4 diisocyanate, tolylene 2,5 diisocyanate, tolylene-2,6-diisocyanate, 1,3-di (isocyanatomethyl) benzene, 1,3-bis (1 isocyanatototo 1-methylethyl ) Benzene and the like.

 [0037] Further, for example, norbornene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 2, 6 tolylene diisocyanate, 2, 4 tolylene diisocyanate, naphthalene 1, 4-diisocyanate, 4, A'-diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, dicyclohexylmethane 4, A'-diisocyanate, 5— Isocyanate 1 (Isocyanate methyl) 1, 3, 3-trimethylcyclohexane, 3, 3 '—Dimethyldiphenylmethane 4, A' — Diisocyanate, xylylene 1,4-diisocyanate, 4, A '-Diphenylpropane diisocyanate diisocyanate, butylene 1,2-diisocyanate, cyclohexylene 1,2-diisocyanate, cyclohexylene 1,4- Jiisoshianeto such leave in the Oh gel that force S such as Isoshianeto.

[0038] Still further, triisocyanates such as 4, Α ', Α "triphenylmethane triisocyanate, toluene 2,4,6-triisocyanate, 4,4'-dimethyldiphenylmethane 2 , 2 ', 5, 5' —tetraisocyanates such as tetraisocyanate, etc. Examples of adducts of cyanate and polyol include trimethylolpropane adduct of hexamethylene diisocyanate, trimethylolpropane adduct of 2,4 tolylene diisocyanate, and trimethylolpropane of xylylene diisocyanate. Isocyanate prepolymers such as adducts and hexanetriol adducts of tolylene diisocyanate can be used. The polyvalent isocyanate compound is not limited to the above compounds, and several kinds of compounds may be used in combination as required.

[(C) Compound containing ethylenic double bond capable of addition polymerization with hydroxyl group in the molecule]

 The compound containing an ethylenic double bond capable of addition polymerization with a hydroxyl group in the molecule is not particularly limited, but preferably 2-hydroxyethyl methacrylate, 2-hin-1,3-dimethacrylate. 2 Hydroxypropylene 1-metatalylate 1-attalylate and the like.

 [0040] These reactions can be carried out in the same manner as a method for synthesizing urethane acrylate by reaction of a normal diol compound, diisocyanate compound, and hydroxyl group-containing acrylate compound.

 [0041] Further, in the reaction products of polyhydric alcohols containing a tertiary amino group in the molecule, diisocyanate compounds, and compounds containing an ethylenic double bond capable of addition polymerization with a hydroxyl group in the molecule. An example is shown below.

[0042] M-1: triethanolamine (1 mol), hexane 1,6 diisocyanate (3 mol),

 2 Hydroxyethyl methacrylate (3 mol) reaction product

 M—2: Reaction product of triethanolamine (1 mol), isophorone diisocyanate (3 mol), 2-hydroxychetyl acrylate (3 mol)

 M—3: N—n Reaction of butyljetanolamine (l mol), 1,3-bis (1 isocyanate 1-methylethinole) benzene (2 mol), 2-hydroxypropylene 1 metatalylate 3 acrylate (2 mol) Product

M—4: N n Butyljetanolamine (1 mol), 1,3-di (isocyanatomethyl) benzene (2 mol), 2-hydroxypropylene 1-metatalylate 1 3-allylate (2 Mol) reaction product

 Reaction product of M-5: N-methyljetanolamine (1 mol), tolylene 2,4-diisocyanate (2 mol), 2 hydroxypropylene 1,3 dimetatalylate (2 mol) Among the obtained reaction products, the compound preferably used in the present invention is preferably dissolved in a solubility of 1% by mass or more in pure water at 25 ° C. More preferably, it is 3% by mass or more, further preferably 5% by mass or more, and particularly preferably 10% by mass or more. By using a compound having such characteristics, the object of the present application can be achieved.

 [0043] In the present invention, among these conventionally known compounds, compounds having specific characteristics can be preferably used. Even more preferably, in addition to the above three components, glycols and the like are used as the fourth component. One of the particularly preferred embodiments is the ability to introduce a non-amino group-containing polyhydric alcohol unit. Specific examples of polyhydric alcohols containing no amino group are listed below.

 [0044] [(d) Polyhydric alcohol containing no amino group]

 Examples of the amino group-free polyhydric alcohol that can be used in the present invention include ethylene glycol, 1,2- or 1,3-propylene glycol, butylene glycol, diethylene glycolanol, triethylene glycolanol, tetraethylene glycolanol, diethylene glycol. Propylene glycol

1,3-- or 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-methylpentanediol, hydrogenated bisphenol mononole A, polyethylene glycolol, polypropylene glycol , Polybutylene glycol, polytetramethylene glycol, poly force prolatatone, trimethylol ethane, trimethylol pronone, polytrimethylone lepronone, pentaerythrinol, polypentaerystinole, sorbitole, mannitol, Polyhydric alcohols such as glycerin and polyglycerin such polyhydric alcohol and maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, adipic acid, phthalic acid, phthalic anhydride, terephthalic acid, isophthalic acid, etc. Reaction with polybasic acids Polyester polyols and, the force Purorataton modified polyols, polyolefin polyols, polycarbonate polyols, polybutadiene polyols, etc. can be mentioned, et al is, they can be used in combination with hydroxy fatty acid esters above. [0045] Further, examples of the polyhydric alcohol compound include 1,3 propanediol, 1,7 heptanediol, 1,8 octanediol, 2,3 dihydroxybutane, 1,2 dihydroxybutane, 1,3 dihydroxybutane, 2,2 dimethyl-1,3 propanediol, 2,4 pentanediol, 2,5-hexanediol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanedimethanol, dihydroxycyclohexane, 1, 2, 6-trihydroxy hexane, phenylene ethylene glycol, 1, 1, 1 trimethylol propane, hexane triol, pentaerythritol, glycerin and other aliphatic polyhydric alcohols, 1, 4-di (2 hydroxy ethoxy) ) Aromatic polyhydric alcohols such as benzene and 1,3 bis (2 hydroxyethoxy) benzene and alkylene oxa P-xylylene glycol, m-xylylene glycol, α, a'-dihydroxy p-diisopropylbenzene, 4, A'-dihydroxydiphenylmethane, 2- (p, p-dihydroxydiphenyl methinole) benzyl alcohol 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenylsulfide, 4, A 'isopropylidenediphenol ethylene oxide adduct, 4,4' isopropylidenediphenol adducted with propylene oxide Thing etc. are mentioned.

 [0046] As a compound to which these fourth components are added,

 M-6: Reaction product of triethanolamine (1 mol), hexane 1,6-diisocyanate (3 mol), 2 hydroxyethyl methacrylate (3 mol), diethylene glycol (3 mol)

 M-7: Reaction product of triethanolamine (1 monole), isophorone diisocyanate (3 mol), 2 hydroxychetyl acrylate (3 mol), ethylene glycol (3 mol)

 M—8: N—n Butyljetanolamine (l mol), 1,3-bis (1 isocyanate 1-methylethinole) benzene (2 mol), 2-hydroxypropylene 1 metatalylate 3 Atarylate (2 mol), diethylene glycol (2 mol) of reaction product

 M 9: N—n Butyljetanolamine (l mol), 1,3-di (isocyanatomethyl) benzene (2 mol), 2 Hydroxypropylene 1-Metatalylate 1-Atalylate (2 mol), Ethylene Reaction product of glycol (2 mol)

M-10: N Methyljetanolamine (1 mol), Tolylene 2, 4 Diisocyanate ( And 2-hydroxypropylene 1,3 dimetatalylate (2 monole) and diethylene glycol (2 mol).

[0047] Another particularly preferred embodiment in the present invention is to keep the mol ratio of the third component, a compound containing an ethylenic double bond capable of addition polymerization with a hydroxyl group in the molecule, low. Specifically, it is a preferred embodiment that the content is preferably controlled to less than 40%, more preferably less than 30%, and particularly preferably less than 25%.

[0048] As compounds having a reduced ratio of the third component,

 M-11: N-n Butyljetanolamine (2 mol), 1,3-bis (1 isocyanato to 1-methylethinole) benzene (3 mol), 2-hydroxypropylene 1 metatalylate 3 acrylate (2 mol) Reaction product

 M-12: Reaction product of N-n-butyljetanolamine (3 moles), hexamethylene diisocyanate (4 monoles), 2 hydroxypropylene 1-methacrylate-3 acrylate (2 monoles)

 M—13: N Ability to list reaction products of methinoresinethanolanol (2 monole), tolylene 2,4 diisocyanate (3 mol), 2 hydroxypropylene 1,3 dimetatalylate (2 mol) S I'll do it.

 [0049] In the present invention, the photosensitive layer contains, among the polymerizable ethylenically unsaturated bond-containing compounds, in particular, a polyfunctional acrylate having an amide bond and a tertiary amino group in one molecule. It is preferable. Here, “polyfunctional” means having a plurality of polymerizable ethylenically unsaturated bonds. In this case, the “multifunctional attalylate having an amide bond and a tertiary amino group in one molecule” preferably has a solid content of 5 to 80 parts by weight, more preferably 15 to 60 parts by weight.

[0050] In addition to the above polymerizable ethylenically unsaturated bond-containing compounds, various polymerizable ethylenically unsaturated bond-containing compounds can be used in combination with the present invention. These polymerizable ethylenically unsaturated bond-containing compounds are not particularly limited, and examples thereof include 2-ethyl hexyl acrylate, 2-hydroxypropyl acrylate, glycerol phenoxy cetyl acrylate, tetrahydrofurfuryl chloride. Shetyl Atarilate, Tetrahi Monofunctional acrylates such as drofurfuroxyhexanolid tallylate, ε-force of 1,3-dioxane alcohol, atalylate of prolatatone adduct, 1,3-dioxolan acrylate Alternatively, methacrylic acid, itaconic acid, crotonic acid, maleic acid esters in which these talates are replaced with metatalates, itaconates, crotonates, and maleates, such as ethylene glycol diatalate, triethylene alcohol diatalate, pentaerythritol diataliate. Hydrate Quinone Ditalylate, Resorcin Ditalylate, Hexanediol Ditalylate, Neopentyl Glycol Ditalylate, Tripropylene Glycono-Resialyl Tallate, Hydropentaline Neopentyl Glycol Diatari Over DOO, neopentyl glycol adipate Jiatarireto, hydroxy Viva Jiatarireto phosphate neopentyl Honoré _ε Ichiriki Purorataton adduct of glycol, 2- (2-hydroxy 1, 1 over dimethylcarbamoyl Honoré ethyl Honoré) 5-hydroxymethyl Roh Leh 5- Echinore 1,3-di-xantia ditalitrate, tricyclodecane dimethylone rare taleate, ε-strength prolatatone adduct of tricyclodecane dimethyl oleorelate, 1,6-hexanediol diglycidyl etherate ditalitrate Bifunctional acrylates such as methacrylic acid, itaconic acid, crotonic acid, maleic acid ester such as trimethylolpropane tritalylate, diacrylate. Limethylol propane tetraatalylate, trimethylolethane tritalylate, pentaerythritol triatolylate, pentaerythritol tetraatalylate, dipentaerythritol tetraatalylate, dipentaerythritol pentaatalylate, dipentaerythritol hexyl Satalylate, dipentaerythritol hexaatalylate ε — force prolatatatone adduct, pyrogallol triatalylate, propionic acid. Dipentaerythritol triatalylate, propionic acid. Dipentaerythritol tetraatalylate, hydroxybivalyl aldehyde Polyfunctional acrylic acid esters such as methylolpropane tritalylate, or these acrylates may be metatalylated, itaconate, crotonate, Examples thereof include metataric acid, itaconic acid, crotonic acid, maleic acid ester and the like in place of maleate.

[0051] As a polymerizable ethylenically unsaturated bond-containing compound, prepolymers can be used in the same manner as described above.

[0052] Examples of the prepolymer include compounds as described later, A prepolymer obtained by introducing acrylic acid or methacrylic acid into a small amount of oligomer and imparting photopolymerizability can also be suitably used.

 [0053] These prepolymers may be used alone or in combination of two or more, and may be used in combination with the above-mentioned monomers and / or oligomers! /.

 [0054] Examples of the prepolymer include adipic acid, trimellitic acid, maleic acid, phthalic acid, terephthalic acid, hymic acid, malonic acid, succinic acid, dartaric acid, itaconic acid, pyromellitic acid, fumaric acid, and glutaric acid. , Pimelic acid, sebacic acid, dodecanoic acid, tetrahydrophthalic acid, and other polybasic acids, ethylene glycol, propylene alcohol, diethylene glycol, propylene oxide, 1,4 butanediole, triethyleneglycolanol, tetraethyleneglycolanol, polyethyleneglycol (Meth) acrylic acid is introduced into a polyester obtained by the combination of polyhydric alcohols such as glycerin, trimethylololepropane, pentaerythritol, sonorebitol, 1,6 hexanediol, 1,2,6 hexanetriol, etc. Polyester atalylates; for example, bisphenolanol ェ -epoxychlorohydrin '(meth) acrylic acid, phenol nopolak' epichrohydrin. (Meth) acrylic acid such as (meth) acrylic acid to epoxy resin Introduced epoxy acrylates; for example, ethylene glycol 'adipic acid' tolylene diisocyanate · 2-hydroxyethyl acrylate, polyethylene glycol metatalylate. Xylene diisocyanate, 1, 2-polybutadiene glycol 'tolylene diisocyanate · 2 —Hydroxyethyl acrylate, trimethylol propane 'propylene glycol. Tolylene diisocyanate. 2—Urethane acrylate with (meth) acrylic acid introduced into urethane resin, such as hydroxyethyl acrylate; policy Siloxane resin acrylates such as loxane acrylate, polysiloxane diisocyanate, 2-hydroxyethyl acrylate, etc .; alkyd modified acrylates in which (meth) attalyloyl groups are introduced into oil-modified alkyd resins, spirane resin acrylates Prepolymers such as rates;

[0055] Further, the polymerizable ethylenically unsaturated bond-containing compound according to the present invention includes phosphazene monomer, triethylene glycol, isocyanuric acid EO (ethylene oxide) -modified diatalylate, isocyanuric acid EO-modified tritalylate, dimethylol trimethylate. Cyclodeca Diatalylate, trimethylolpropane acrylic acid benzoate, alkylene diol type acrylic acid modified monomers such as urethane modified acrylate, and addition polymerizable oligomers and prepolymers having structural units formed from such monomers Can be mentioned.

 [0056] In addition, JP-A 58-212994, 61-6649, 62-46688, 62-48589, 62-173295, 62-187092 The compounds described in JP-A-63-367189, JP-A-1-244891, etc., and the compounds described in “Chemical Products of 11290”, Chemical Industry Daily, p. 286 to p.294. The compounds described in “UV'EB Curing Handbook (Raw Materials)”, Kobunshi Kankokai, p. 1;! -65 can also be used in the present invention.

[0057] The content of the polymerizable ethylenically unsaturated bond-containing compound according to the present invention in the photosensitive layer is preferably in the range of 1.0 to 80.0 mass% with respect to the solid content of the photosensitive layer. Guyori preferred properly is in the range of 3. 0-70. 0 wt ^_0/0.

 [0058] (Photopolymerization initiator)

 In the photosensitive lithographic printing plate material of the present invention, the photosensitive layer is required to contain a polymerization initiator. The polymerization initiator is a compound capable of initiating polymerization of a polymerizable ethylenically unsaturated bond-containing compound upon image exposure. For example, a biimidazole compound, an iron arene complex compound, a titanocene compound, a polyhalogen compound, a monohalogen compound, or the like. Alkyl triaryl phosphate compounds are preferably used. Of these, biimidazole compounds and iron arene complexes are preferably used.

 [0059] The biimidazole compound is a derivative of biimidazole, and examples thereof include compounds described in JP-A-2003-295426.

 [0060] In the present invention, a hexaarylbiimidazole (a dimer of triarylimidazole) compound can be preferably used as the biimidazole compound.

[0061] Processes for the production of moss are described in German patents (DE1, 470, 154) and their use in photopolymerizable compositions is described in European patents (ΕΡ24,629), European patents ( EP10 7, 792), US patent (US4, 410, 621), European patent (EP215, 453) and German patent (DE3, 211, 312) are described. [0062] Preferable biimidazole compounds include, for example, 2, 4, 5, 2 ', 4', 5'-hexaphen-2-noreviimidazole, 2,2'-bis (2 black mouth phenyl) 1, 4, 5 , A ', 5' — Tetraphenyl dibiimidazole, 2, 2 '— Bis (2 bromophenyl) 1, 4, 5, A', 5 '— Tetraphenyl biimidazole, 2, 2' — Bis (2, 4 Dichlorophenol) 1, 4, 5, A ', 5' — Tetraf Eneno Levi imidazonole, 2, 2 '— Bis (2 black mouth Fuenore) 1, 4, 5, 4', 5 '— Tetrakis (3 methoxyphenyl) biimidazole, 2, 2 'bis (2 chlorophenyl) 4, 5, 4', 5 '—tetrakis (3, 4, 5 trimethoxyphenyl) monobiimidazole, 2, 5, 2 ', 5' — Tetrakis (2 black mouth phenyl) 1, 4 '— Bis (3,4 dimethoxyphenyl) biimidazole, 2, 2' — Bis (2, 6 dichlorophenyl) 1 4 , 5, A ', 5' — Troughphenylbiimidazole, 2, 2 '— Bis (2nitrophenyl) 1, 4, 5, 4', 5 '— Tetrafe: ^

 Biimidazonole, 2, 2 '— Diol o Torinore 1, 5, 5, A', 5 '— Tetraphenylenobiimidazole, 2, 2' — Bis (2 ethoxyphenyl) 4, 5, A ', 5'-tetraphenylbiimidazole and 2,2'-bis (2,6 difluorophenyl) 4, 5, A ', 5'-tetraphenylbiimidazole. These compounds are available as commercial products. it can.

 [0063] The content of the biimidazole compound is preferably 0.05% by mass to 20.0% by mass with respect to the solid content of the photosensitive layer. 1.0% by mass to 10.0% by mass is particularly preferable. preferable. The ratio of the content of the dye represented by the general formula (1) and the biimidazole compound (dye / biimidazole (mass ratio)) is preferably 0.0;! -20, and particularly preferably 0.1- 10 is preferred.

 [0064] As the polymerization initiator, in addition to the biimidazole compound, another polymerization initiator may be used in combination.

 [0065] Examples of these polymerization initiators include titanocene compounds, monoalkyltriaryl phosphate compounds, iron arene complex compounds, polyhalogen compounds, and the like.

[0066] Examples of the titanocene compound include compounds described in JP-A-63-41483 and JP-A-2-291. More preferable specific examples include bis (cyclopentagenyl) Ti dimonochloride. Bis (cyclopentadienyl) Ti bis monophenyl, bis (cyclopentaenyl) ti Ti bis 1, 3, 4, 5, 6 pentafluorophenyl, bis (cyclopentaenyl) ti Ti bis 1, 3, 5, 6 Tetrafluorophenyl, bis (cyclopenta Genyl) 1 Ti bis 1, 2, 4, 6 trifluorophenyl, bis (cyclopentaenyl) — Ti bis 1, 2, 6 difluorophenyl, bis (cyclopentadienyl) 1 Ti bis 1, 2, 4-difluorophenyl Bis (methylcyclopentagenyl) Ti-bis 2,3,4,5,6 pentafluorophenyl, bis (methylcyclopentadenyl) one Ti bis-1,2,5,5,6-tetrafluorophenyl, Bis (methylcyclopentadienyl) 1 Ti Bis 1 2, 6 Difluorophenol (IRUGACURE727L: Ciba Specialty Chemicals), Bis (cyclopentagenyl) 1 Bis (2, 6 Difluoro 1- 3 1—yl) phenyl) titanium (IRUGACURE784: Tino 'Specialty Chemicals), bis (cyclopentageninore) bis (2, 4, 6 trifnorero 3 (Pilly 1- Inole) Fe Ninore) Titanium bis (cyclopentagenyl) bis (2, 4, 6 trifluoro-3- (2-5-dimethylpyridyl) phenyl) titanium and the like.

 [0067] Examples of the monoalkyl triaryl porate compound include JP-A-62-150242 and JP-A-62.

 The compounds described in No. 143044 and the like, but more preferred specific examples include tetral n butylammonium η butyl-trinaphthalene 1-rubolate, tetra η butylammonium η butyl-triphenyl rubrate, tetra η Butinoleammonium η butyltolylate (4-tert-butylphenyl) -borate, tetra-n-butylammonium η-hexylate (3-chloro-4-methylphenyl) -borate, tetra-η butylammonium η-hexoxyrootry (3-fluorophenyl) ) -Borate and the like.

 [0068] Examples of the iron arene complex include compounds described in JP-A-59-219307. More preferred specific examples include η benzene mono (7) -cyclopentagenenyl) iron hexafluorophosphate 7] -cumene mono (7) -cyclopentageninole) iron hexafluorophosphate, 7] -fluorene mono (7) -cyclopentageninole) iron hexafluorophosphate, J] naphthalene mono (7)- Cyclopentagenino) iron hexanoleophosphate phosphate, Τ] -xylene mono (η-cyclopentageninole) iron hexanoleophosphate, η benzene mono (7) -cyclopentagenenyl) iron tetrafluorobo Rate and the like.

[0069] As the polyhalogen compound, a compound having a trihalogenmethyl group, a dihalogenmethyl group or a dihalogenmethylene group is preferably used, and particularly represented by the following general formula (1). And rosogen compounds and compounds in which the above group is substituted on the oxadiazole ring are preferably used.

 [0070] Of these, halogen compounds represented by the following general formula (2) are particularly preferably used.

[0071] General formula (1) R ¹ — CY— (C = ○) one R ²

In the formula, R ¹ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an acyl group, an alkenylsulfonyl group, an arylsulfonyl group, an iminosulfonyl group, or a cyan group.

R ² represents a monovalent substituent. R ¹ and R ² may combine to form a ring. Y represents a halogen atom.

[0072] General Formula (2) CY— (C = 〇) One X— R ³

In the formula, R ³ represents a monovalent substituent. X represents O NR ^4. R ⁴ represents a hydrogen atom or an alkyl group. Even if R ³ and R ⁴ combine to form a ring, there is no force. Y represents a halogen atom. Of these, those having a polyhalogenacetylamide group are particularly preferred.

 [0073] A compound in which a polyhalogenmethyl group is substituted on the oxadiazole ring is also preferably used. Further, oxaziazole compounds described in JP-A-5-34904 and 8-240909 are also preferably used.

 [0074] In addition, any polymerization initiator can be used in combination. For example, carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo and diazo compounds, halogens, as described in Chapter 5 of “Light Sensitive Systems” by J. Kosar. Examples thereof include compounds and photoreducible dyes. More specific compounds are disclosed in British Patent 1,459,563.

 That is, as a polymerization initiator that can be used in combination, the following can be used.

[0076] Benzoin derivatives such as benzoin methyl ether, benzoin i-propyl ether, α, α-dimethoxy-a-phenylacetophenone; benzophenone, 2,4 dichlorobenzophenone, o methyl benzoylbenzoate, 4, Α ' Benzophenone derivatives such as bis (dimethylamino) benzophenone; 2-thiaxanthone derivatives such as 2-clothiaxanthone, 2-i-propylthixanthone; 2-clothalanthraquinones, 2-methylanthraquinones Anthraquinone derivatives such as N-methyl attaridone, N-butyl attaridone etc. Ataridon derivatives such as α, a-diethoxyacetophenone, benzyl, fluorenone, xanthone, ura ninolei compound, and Japanese special day Triazine derivatives described in 59-1281, 61-9621 and JP-A-60-60104; organic peroxides described in JP-A-59-1504 and 61-243807; , 44-6413, 44-6413, 47-1604 and US Patent 3,567,453; US Patents 2,848,328, 2,852,379 And organic azide compounds described in JP 2,940,853; o-quinonediazides described in JP-B-36-22062b, 37-13109, 38-18015 and 45-9610; Special Japanese Day Call 55-39162, Japanese Patent Laid-Open No. 59-14023 and “Macro Molecules (M acromolecules), Vol. 10, p. 1307 (1977); various onium compounds; JP-A-59-142205, azo-compounds; JP-A-1-54440, European Patents 109,851, 126,712 No. and "Journal 'Ob' Imaging Science (J. Imag. Sci.)", Volume 30, page 174 (1986); Japanese Patent Application No. 4-56831 (Japanese Patent Laid-Open No. 5-213861) ) And 4-89535 (Japanese Patent Laid-Open No. 5-255 347); “Oxosulfonium organoboron complex”; “Coordination Chemistry Review”, 84, 85-277 (1988). And transition metal complexes containing a transition metal such as ruthenium described in JP-A-2-182701; 2,4,5-triarylimidazole dimer described in JP-A-3-209477; carbon tetrafluoride, JP Organic halogen compounds described in Sho 59-107344, etc.

 [0077] The content (total amount) of the polymerization initiator is preferably 0.05% by mass to 20.0% by mass with respect to the solid content of the photosensitive layer. 1.0% by mass to 10.0% by mass Is particularly preferred.

 [0078] (Spectral sensitizer)

 The photosensitive layer according to the present invention preferably contains at least a spectral sensitizer having an absorption maximum wavelength of 350 to 450 nm as a spectral sensitizer! /.

[0079] The spectral sensitizer includes, for example, cyanine, merocyanine, porphyrin, spiro compound, Hue mouth sen, fluorene, fulgide, imidazonole, perylene, phenazine, phenothiazine, atalidine, attaridone, azo compound, diphenylmethane, triflic acid. Enylmethane, triphenylamine, coumarin derivatives, quinacridone, indigo, styryl, pyrylium compounds, Examples include lomethene compounds, pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, thiobarbituric acid derivatives, and ketoalcohol borate complexes.

 [0080] Examples of the above-mentioned coumarin derivatives include the coumarin derivatives B-1 to B-22 in JP-A-8-129258, the D-1 force of JP2003-21901, and the coumarins of D-32. Inductives, one force of JP 2002-363206 Koyuki, et al. 21 Coumadin derivatives, one force of JP 2002-363 207 Koyuki, et al. 40 coumarin derivatives, one force of JP 2002-363208 Koyuki, et al. 34 coumarin derivatives, 1 to 56 coumarin derivatives of JP-A-2002-363209 and the like can be mentioned, and these can be preferably used.

 [0081] Other preferable dyes that can be used include, for example, JP-A 2000-98605, JP-A 2000-147763, JP-A 2000-206690, JP-A 2000-258910, and JP-A 2000-309724. And spectral sensitizers described in JP-A No. 2001-042524, JP-A No. 2002-202598, JP-A No. 2000-22 1790, and the like.

 [0082] (Polymer binder)

 The polymer binder according to the present invention can carry the components contained in the photosensitive layer on a support. Examples of the polymer binder include acrylic polymers, polybutylpropylene resins, polyurethane resins, Polyamide resin, polyester resin, epoxy resin, phenol resin, polycarbonate resin, polybutyl butyral resin, polybulal formal resin, shellac, and other natural resins can be used. Also, using two or more of these in combination does not help.

 [0083] Preferably, a bull copolymer obtained by copolymerization of an acrylic monomer is preferred. Furthermore, the copolymer composition of the polymer binder is preferably a copolymer of (a) a carboxylene group-containing monomer, (b) a methacrylic acid alkyl ester, or an acrylic acid alkyl ester.

[0084] Specific examples of the carboxyl group-containing monomer include α, / 3-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, and itaconic anhydride. In addition, carboxylic acids such as half esters of phthalic acid and 2-hydroxymetatalylate are also preferred. [0085] Specific examples of the alkyl methacrylate and the alkyl acrylate include methyl methacrylate, ethyl acetate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, heptyl methacrylate, To octyl methacrylate, Noel methacrylate, decyl methacrylate, undecyl methacrylate, dodecyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, acrylic acid In addition to unsubstituted alkyl esters such as butyl, octyl acrylate, nonanol acrylate, decyl acrylate, undecyl acrylate, dodecyl acrylate, and the like, cyclic alcohols such as cyclohexyl methacrylate and cyclohexyl acrylate Ester, benzyl methacrylate, methacrylate-2-chloroethyl, N, N-dimethylaminoethyl methacrylate, glycidyl methacrylate, benzyl acrylate, acrylate--2-chloroethyl, N, N-dimethylaminoethyl Examples thereof also include substituted alkyl esters such as acrylate and glycidyl acrylate.

 [0086] Further, in the polymer binder, the monomers described in the following (1) to (; 14) can be used as a copolymerization monomer.

 [0087] 1) Monomers having an aromatic hydroxyl group, such as o- (or p-, m-) hydroxystyrene, o- (or p-, m-) hydroxyphenyl acrylate.

 [0088] 2) Monomers having an aliphatic hydroxyl group, such as 2-hydroxyethyl talylate, 2-hydroxychetyl methacrylate, N-methylol acrylamide, N-methylol methacrylate, 4-hydroxybutyl methacrylate , 5-hydroxypentyl acrylate, 5-hydroxypentyl methacrylate, 6-hydroxyhexyl acrylate, 6-hydroxy hexyl methacrylate, N- (2-hydroxyethyl) acrylamide, N- (2 —Hydroxyethyl) methacrylamide, hydroxyethyl butyl ether and the like.

 [0089] 3) A monomer having an aminosulfonyl group, for example, m- (or p-) aminosulfonylphenyl metatalylate, m- (or p-) aminosulfuryl phenyl acrylate, N- (p- aminosulfuryl) Phenyl) methacrylamide, N- (p-aminosulfurphenyl) atalinoleamide and the like.

[0090] 4) Monomers having a sulfonamide group, such as N- (p-toluenesulfonyl) acrylamide, N- (p-toluenesulfonyl) methacrylamide and the like. [0091] 5) Acrylamide or methacrylamides, such as acrylamide, methacrylamide, N-ethyl acrylamide, N-hexyl acrylamide, N cyclohexyl acrylamide, N-phenyl acrylamide, N- (4-nitrophenyl) acrylamide, N-ethyl N-phenyl acrylamide, N- (4-hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) methacrylolamide and the like.

 [0092] 6) Monomers containing fluorinated alkyl groups, such as trifluoroethyl allylate, tri-lopinole methacrylate, otata foleno pentenorea taleate, otaf foleno pentenore methacrylate, hepta Decafluorodecyl metatalylate, N Butyl N— (2—Atari mouth

[0093] 7) Butyl ethers, for example, ethyl butyl ether, 2 chloroethyl vinyl ethereole, propinorevininoreethenore, butinorevininoreethenore, otachinolevininoreethenore

, Vinyl vinyl ether, etc.

[0094] 8) Bull esters, for example, bull acetate, bull black mouth acetate, bull butyrate, bull benzoate and the like.

[0095] 9) Styrenes such as styrene, methylstyrene, chloromethylstyrene and the like.

[0096] 10) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinylol ketone, and phenyl vinyl ketone.

[0097] 11) Olefins, such as ethylene, propylene, i-butylene, butadiene, and isoprene.

 [0098] 12) N-Bulpyrrolidone, N-Bulcarbazole, 4-Burpyridine and the like.

[0099] 13) Monomers having a cyano group, such as acrylonitrile, methatalonitrile, 2-pentenenitryl, 2-methyl-3-butenenitryl, 2-cyanoethyl acrylate, o (or m-, p) cyanostyrene, etc. .

[0100] 14) Monomers having an amino group, for example, N, N dimethylaminoethyl methacrylate, N, N dimethylaminoethyl acrylate, N, N dimethylaminoethyl methacrylate, polybutadiene urethane acrylate, N, N Dimethylaminopropyl acrylamide, N, N dimethyl acrylamide, Ataliroyl morpholine, N—i propyl acrylamide, N, N Jetylacrylamide, etc.

[0101] Furthermore, other monomers that can be copolymerized with these monomers may be copolymerized.

[0102] Furthermore, the polymer binder is preferably a bull polymer having a carboxyl group and a polymerizable double bond in the side chain. For example, an unsaturated bond-containing bulle copolymer obtained by addition-reacting a compound having a (meth) atalyloyl group and an epoxy group in a molecule to a carboxyl group present in the bulle copolymer molecule. Polymers are also preferred as high molecular binders.

[0103] Specific examples of compounds containing both an unsaturated bond and an epoxy group in the molecule include glycidyl acrylate, glycidyl methacrylate, and epoxy group-containing unsaturated compounds described in JP-A-11-271969. Compounds and the like. There is also an unsaturated bond-containing bulle copolymer obtained by addition-reacting a compound having a (meth) attalyloyl group and an isocyanate group in the molecule to the hydroxyl group present in the bulle polymer. Preferred as a polymer binder. Compounds having both an unsaturated bond and an isocyanate group in the molecule include burisocyanate, (meth) acrylic isocyanate, 2— (meth) atariloy noroxechinoreisocyanate, m—or p —Isopropeninole α, α ′ — Dimethinole benzyl isocyanate is preferred (meth) acrylic isocyanate, 2- (meth) atariloy noroxetyl isocyanate, and the like.

 [0104] The bull polymer having a carboxyl group and a polymerizable double bond in the side chain is preferably 50 to 100% by mass, more preferably 100% by mass in the total high molecular binder. .

 [0105] The content of the polymer binder in the photosensitive layer is preferably in the range of 10 to 90% by mass 1

The range of 5 to 70% by mass is more preferred. The use in the range of 20 to 50% by mass is particularly preferred from the viewpoint of sensitivity.

[0106] (Various additives)

 In the photosensitive layer according to the present invention, in addition to the above-described components, in order to prevent unnecessary polymerization of an ethylenic double bond monomer that can be polymerized during the production or storage of the photosensitive lithographic printing plate material, It is desirable to add a polymerization inhibitor!

[0107] Suitable polymerization inhibitors include hydroquinone, ρ methoxyphenol, di-tert-butylene. p Crezo monore, pyrogalonore, t-butinore force Teconole, benzoquinone, 4, 4'-thiobis (3 methyl-6-t butylphenol), 2, 2'-methylenebis (4-methyl-6-t butylphenol), N nitrosophenyl hydroxyl Amine primary cerium salt, 2-t-butynole 6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate.

 [0108] The addition amount of the polymerization inhibitor is preferably about 0.01% to about 5% with respect to the total solid content of the photosensitive layer. If necessary, higher fatty acid derivatives such as behenic acid and behenic acid amide may be added to prevent polymerization inhibition by oxygen, or it may be unevenly distributed on the surface of the photosensitive layer during the drying process after coating. Also good. The amount of the higher fatty acid derivative added is preferably from about 0.5% to about 10% of the total composition.

 [0109] In addition, a colorant can also be used, and as the colorant, conventionally known ones including commercially available ones can be suitably used. For example, those described in the revised new edition “Handbook of Pigments”, edited by the Japan Pigment Technology Association (Seibundo Shinkosha), Color Index Handbook, etc.

 [0110] Examples of pigments include black pigments, yellow pigments, red pigments, brown pigments, purple pigments, blue pigments, green pigments, fluorescent pigments, and metal powder pigments. Specific examples include inorganic pigments (titanium dioxide, carbon black, graphite, zinc oxide, Prussian blue, sulfidizing power domum, iron oxide, and lead, zinc, normic and calcium chromates) and organic pigments ( And azo dyes, thioindigo, anthraquinone, anthanthrone, and triphendioxazine pigments, vat dye pigments, phthalocyanine pigments and derivatives thereof, and quinatalidone pigments.

 [0111] Among these, it is preferable to select and use a pigment that has substantially no absorption in the absorption wavelength region of the spectral sensitizing dye corresponding to the exposure laser to be used. It is preferable that the reflection / absorption of the pigment using an integrating sphere is 0.05 or less. Further, the addition amount of the pigment is preferably from 0.2 to 10% by mass, more preferably from 0.2 to 5% by mass based on the solid content of the composition.

[0112] From the viewpoints of pigment absorption in the above-mentioned photosensitive wavelength region and visible image properties after development, it is preferable to use a violet pigment or a blue pigment. These include, for example, cobalt blue, cenoleol bunolei, alkali blue rake, fonatone blue 6g, victoria blue Metal, phthalocyanine blue, phthalocyanine blue first sky blue, indanthrene bunoley, indico, dioxane violet, isoviolanthrone violet, indanthrone blue, indanthrone BC it can. Of these, phthalocyanine blue and dioxane violet are more preferable.

 [0113] Further, the photosensitive layer can contain a surfactant as a coating property improving agent as long as the performance of the present invention is not impaired. Of these, fluorine-based surfactants are preferred.

 [0114] In order to improve the physical properties of the cured film, additives such as plasticizers such as dioctyl phthalate, dimethyl phthalate, and tricresyl phosphate may be added. These addition amounts are preferably 10% or less of the total solid content.

 [0115] The solvent used in preparing the photosensitive layer coating solution of the photosensitive layer according to the present invention includes, for example, alcohol: polyhydric alcohol derivatives such as sec-butanol, isobutanol, n-hexanol. , Penzinoreanolo Conole, Diethylene Glycol Nole, Triethylene Glycol, Tetraethylene Daricol, 1,5-Pentanediol, Ethers Preferred examples include tenole, tripropylene glycol monomethyl ether, ketones, aldehydes: diacetone alcohol, cyclohexanone, methylcyclohexanone, and esters: ethyl lactate, lactyl butyl, jetyl oxalate, and methyl benzoate.

 Although the photosensitive layer coating solution has been described above, the photosensitive layer according to the present invention is constituted by coating on a support using the photosensitive layer.

[0117] photosensitive layer according to the present invention as the amount per on the ^{support, 0. lg / m 2 ~;} 10g / m 2 is preferred lay especially ^{0. 5g / m 2 ~5g / m} 2 is preferred.

 [0118] (Protective layer (oxygen barrier layer))

 A protective layer can be provided on the upper side of the photosensitive layer according to the present invention, if necessary.

 [0119] The protective layer (oxygen barrier layer) preferably has high solubility in a developer solution (generally an alkaline aqueous solution) to be described later. Specifically, polybutyl alcohol and polybutylpyrrolidone are mentioned. S can. Polybulol alcohol has the effect of suppressing the permeation of oxygen, and polybulurpyrrolidone has the effect of ensuring adhesion with the adjacent photosensitive layer.

[0120] In addition to the above two polymers, polysaccharides, polyethylene glycol, Gelatin, glue, casein, hydroxyethinoresenololose, strong noreoxymethinoresenololose, methylcellulose, hydroxyethyl starch, gum arabic, sucrose octacetate, ammonium alginate, sodium alginate, polybulamine, polyethyleneoxide It is also possible to use water-soluble polymers such as polystyrene sulfonic acid, polyacrylic acid, and water-soluble polyamide in combination.

 [0121] When a protective layer is provided on the photosensitive lithographic printing plate of the present invention, the peel force between the photosensitive layer and the protective layer is preferably ¾5 mN / mm or more, more preferably 50 mN / mm or more. Is more than 75mN / mm. Preferred examples of the protective layer composition include those described in Japanese Patent Application No. 8-161645 (Japanese Patent Laid-Open No. 10-010742).

 [0122] The peeling force in the present invention is such that an adhesive tape having a predetermined width having a sufficiently large adhesive force is applied on the protective layer, and then peeled off with the protective layer at an angle of 90 degrees with respect to the plane of the photosensitive lithographic printing plate material. It can be obtained by measuring the force when doing.

 [0123] The protective layer may further contain a surfactant, a matting agent and the like as required.

 The above protective layer composition is dissolved in a suitable solvent, applied onto the photosensitive layer and dried to form a protective layer. The main component of the coating solvent is particularly preferably water or an alcohol such as methanol, ethanol or i-propanol.

 [0124] When the protective layer is provided, the thickness is preferably 0 ·;! ~ 5 · 0 m, particularly preferably 0 · 5 ~

3. 0 μm.

[0125] (Support)

 The support according to the present invention is a plate or film capable of carrying a photosensitive layer, and preferably has a hydrophilic surface on the side where the photosensitive layer is provided.

[0126] As the support according to the present invention, for example, a metal plate such as aluminum, stainless steel, chromium or nickel, or a plastic film such as polyester film, polyethylene film or polypropylene film laminated or vapor-deposited with the above-mentioned metal thin film or the like. Can be mentioned.

 [0127] In addition, a force S that can be used such as a polyester film, a chlorinated chloride film, a nylon film having a surface subjected to a hydrophilization treatment, and an aluminum support are preferably used.

[0128] In the case of an aluminum support, pure aluminum or an aluminum alloy is used. [0129] Various aluminum alloys can be used as the support, for example, silicon, copper, mangan, magnesium, chromium, zinc, lead, bismuth, nickel, titanium, sodium, iron, and other metals and aluminum. An alloy is used. In addition, the aluminum support having a roughened surface is used for water retention.

 [0130] When an aluminum support is used, it is preferable to perform a degreasing treatment in order to remove the rolling oil on the surface prior to roughening (graining treatment). As the degreasing treatment, a degreasing treatment using a solvent such as tritalene or thinner, an emulsion degreasing treatment using an emulsion such as kesilon or triethanol, or the like is used. An alkaline aqueous solution such as caustic soda can also be used for the degreasing treatment. When an alkaline aqueous solution such as caustic soda is used for the degreasing treatment, dirt and oxide film that cannot be removed only by the above degreasing treatment can be removed. When an alkaline aqueous solution such as caustic soda is used for the degreasing treatment, smut is generated on the surface of the support. In this case, the substrate is immersed in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid, or a mixed acid thereof. It is preferable to apply a desmut treatment. Examples of the roughening method include a mechanical method and a method of etching by electrolysis.

 [0131] The mechanical surface roughening method used is not particularly limited, but a brush polishing method and a Houng polishing method are preferable.

 [0132] The electrochemical surface roughening method is not particularly limited, but a method of electrochemical surface roughening in an acidic electrolyte is preferable.

 [0133] After the surface is roughened by the electrochemical surface roughening method, it is preferably immersed in an aqueous solution of acid or alkali in order to remove aluminum scraps on the surface. Examples of the acid include sulfuric acid, persulfuric acid, hydrofluoric acid, phosphoric acid, nitric acid, hydrochloric acid, and the like. Examples of the base include sodium hydroxide, potassium hydroxide, and the like. Among these, it is preferable to use an alkaline aqueous solution.

[0134] The dissolution amount of aluminum in the plate surface, 0. 5~5g / m ² is preferred. In addition, it is preferable that after the immersion treatment with an alkaline aqueous solution, neutralization treatment is performed by immersion in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid or a mixed acid thereof.

[0135] The mechanical surface roughening method and the electrochemical surface roughening method may each be used alone for surface roughening, or the mechanical surface roughening method followed by the electrochemical surface roughening method. To roughen the surface May be.

 [0136] Following the roughening treatment, an anodizing treatment can be performed. As the anodizing treatment method that can be used in the present invention, a known method without particular limitation can be used. By performing the anodizing treatment, an oxide film is formed on the support.

 [0137] The anodized support may be sealed as necessary. These sealing treatments can be performed using known methods such as hot water treatment, boiling water treatment, steam treatment, sodium silicate treatment, dichromate aqueous solution treatment, nitrite treatment, and ammonium acetate treatment.

Yes

 [0138] Further, after these treatments, water-soluble resins such as polybuluphosphonic acid, polymers and copolymers having sulfonic acid groups in the side chain, polyacrylic acid, water-soluble metal salts (for example, Zinc borate) or a primer coated with a yellow dye, an amine salt or the like is also suitable. Furthermore, a sol-gel treated substrate in which a functional group capable of causing an addition reaction by a radical as disclosed in JP-A-5-304358 is covalently used.

 [0139] (Application)

 The above photosensitive layer coating solution can be coated on a support by a conventionally known method and dried to prepare a photosensitive lithographic printing plate material.

[0140] Examples of the coating method of the coating liquid include air doctor coater method, blade coater method, wire bar method, knife coater method, dip coater method, reverse roll coater method, gravure coater method, cast coating method, curtain coater method and extrusion method. Examples include the coater method.

 [0141] As the solvent used in preparing the coating solution for the photosensitive layer, propylene glycol monomethinoreethenole, cyclohexanone, methinoreethinoleketone, propyleneglycololemonomethyl ether acetate, etc. may be used. In particular, propylene glycol monomethyl ether is preferred in the present invention!

[0142] The drying temperature of the photosensitive layer is preferably from 60 to 160 ° C, more preferably from 80 to 140 ° C, and particularly preferably from 90 to 120 ° C.

[0143] (Image exposure)

The light source for recording an image on the photosensitive lithographic printing plate material of the present invention has an emission wavelength of 370. The use of ~ 440 nm laser light is preferred.

[0144] As a light source for exposing the photosensitive lithographic printing plate of the present invention, for example, a He-Cd laser (

 441nm), Cr: LiSAF and SHG crystal combination as solid laser (430nm), Semiconductor laser system as KNbO, ring resonator (430nm), AlGaInN (350nm ~ 450nm), AlGalnN semiconductor laser (Semiconductor laser 400-410nm) etc.

 [0145] In the case of laser exposure, light can be narrowed down in the form of a beam, and scanning exposure according to image data is possible, so it is suitable for direct writing without using a mask material.

 [0146] When a laser is used as a light source, it is easy to reduce the exposure area to a very small size, and high-resolution image formation is possible.

 [0147] Laser scanning methods include cylindrical outer surface scanning, cylindrical inner surface scanning, and planar scanning. In the cylindrical outer surface scanning, one exposure of the laser is performed while rotating the drum around which the recording material is wound, the rotation of the drum is the main scanning, and the movement of the laser beam is the sub scanning. In cylindrical inner surface scanning, a recording material is fixed to the inner surface of the drum, a laser beam is irradiated from the inside, and part or all of the optical system is rotated to perform main scanning in the circumferential direction. Alternatively, the whole is linearly moved parallel to the drum axis to perform sub-scanning in the axial direction. In plane scanning, the main scanning of laser light is performed by combining a polygon mirror, galvanometer mirror, and fΘ lens, and sub-scanning is performed by moving the recording medium. Cylindrical outer surface scanning and circular cylinder inner surface scanning are suitable for high-density recording that facilitates increasing the accuracy of the optical system.

[0148] In the present invention, it is preferable that image exposure is performed with a plate surface energy (energy on the plate material) of 10 mj / cm ² or more, and the upper limit is 500 mj / cm ² . More preferably, it is 10 to 300 mj / cm ² . For this energy measurement, for example, a laser power meter PDGDO-3W manufactured by OphirOptronics can be used.

 [0149] (Developer)

 The exposed portion of the photosensitive layer subjected to image exposure is cured. This is preferably developed with an alkaline developer to remove the unexposed areas and form an image.

[0150] As such a developer, a conventionally known alkaline aqueous solution can be used. For example, sodium silicate, potassium, ammonium; dibasic sodium phosphate, potassium, Sodium bicarbonate, potassium, ammonium, sodium carbonate, potassium, ammonium, sodium bicarbonate, potassium, ammonium, sodium borate, potassium, ammonium, sodium hydroxide, potassium, ammonium And an alkaline developer using an inorganic alkali agent such as lithium.

 [0151] In addition, monomethylamine, dimethylamine, trimethylamine, monoethylamine, jetylamine, triethylamine, mono-1-propylamine, di-1-propylamine, tri-1-propylamine, butylamine, monoethanolamine, diethanolamine Organic alkali agents such as triethanolamine, mono-i-propanolamine, di-i-propanolamine, ethyleneimine, ethylenediamine and pyridine can also be used.

 [0152] These alkaline agents may be used alone or in combination of two or more. Further, an organic solvent such as an anionic surfactant, an amphoteric surfactant or alcohol can be added to the developer as necessary.

 [0153] The alkaline developer can also be prepared from a developer concentrate such as granules and tablets.

 [0154] The developer concentrate may be once evaporated into a developer and evaporated to dryness, but preferably the material is added by adding a small amount of water without adding water when mixing a plurality of materials. A method of concentrating the mixture to obtain a concentrated state is preferable. The developer concentrates are disclosed in JP-A-51-61837, JP-A-2-109042, JP-A-2-109043, JP-A-3-39735, JP-A-5-142786, JP-A-6-266062, — Granules and tablets can be obtained by a well-known method described in No. 13341 or the like. The developer concentrate can also be divided into multiple parts with different material types and ratios! /.

 [0155] The alkaline developer and its replenisher may further contain a preservative, a colorant, a thickener, an antifoaming agent, a hard water softening agent, and the like, if necessary.

 [0156] (Automatic processor)

It is advantageous to use an automatic processor for developing the photosensitive lithographic printing plate material. An automatic image processor is preferably provided with a mechanism for automatically supplying a required amount of developer replenisher to the developing bath, and preferably a mechanism for discharging a developer exceeding a certain amount is preferably provided. In addition, a mechanism for automatically replenishing a required amount of water to the developing bath is provided, and preferably a mechanism for detecting plate passing is provided. Preferably, the processing area of the plate is based on detection of plate passing. A mechanism for controlling the replenishment amount and / or replenishment timing of the replenisher solution and / or water to be replenished preferably based on the detection of the printing plate and / or the estimation of the processing area is provided. Preferably, a mechanism for controlling the temperature of the developer is added, preferably a mechanism for detecting the pH and / or conductivity of the developer is provided, preferably the pH and / or of the developer. Or, a mechanism for controlling the amount and / or timing of the replenisher and / or water to be replenished based on the conductivity is provided! Further, it preferably has a function of once diluting and stirring the developer concentrate with water. If there is a washing step after the development step, use the washing water after use as dilution water for the concentrate of the development concentrate.

 [0157] The automatic processor may have a pretreatment section for immersing the plate in the pretreatment liquid before the development step. The pretreatment section is preferably provided with a mechanism for spraying the pretreatment liquid onto the plate surface, and preferably provided with a mechanism for controlling the temperature of the pretreatment liquid to an arbitrary temperature of 25 to 55 ° C. Preferably, a mechanism for rubbing the plate surface with a roller-like brush is provided. Water or the like is used as the pretreatment liquid.

 [0158] (Post-processing)

 The lithographic printing plate material developed with an alkaline developer is subjected to post-treatment with washing water, a rinsing solution containing a surfactant, a fischer or a protective gum solution mainly composed of gum arabic or starch derivatives. Is done. These treatments can be used in various combinations, for example, development → washing → treatment of rinsing liquid containing surfactant and development → water washing → finisher with one liquid is preferable because the rinse liquid has less fatigue of the Fischer liquid. . Furthermore, countercurrent multistage treatment using a rinse liquid or a finish liquid is also preferred.

[0159] These post-processing are generally performed using an automatic developing machine including a developing unit and a post-processing unit. As the post-treatment liquid, a method of spraying from a spray nozzle or a method of immersing and conveying in a treatment tank filled with the treatment liquid is used. In addition, a method is also known in which a certain amount of a small amount of washing water is supplied to the plate surface after development, and the waste solution is reused as dilution water for the developing solution stock solution. In such automatic processing, each processing solution can be processed while being replenished with each replenisher according to the processing amount, operating time, and the like. In addition, a so-called disposable treatment method in which treatment is performed with a substantially unused post-treatment liquid is also applicable. By such processing The obtained lithographic printing plate is loaded on an offset printing machine and used for printing a large number of sheets. Example

 [0160] Hereinafter, the ability to explain the present invention in detail with reference to examples is not intended to limit the embodiments of the present invention. In the examples, “parts” represents “parts by mass” unless otherwise specified.

 <Preparation of photosensitive lithographic printing plate>

 (Preparation of support 1)

 A 0.3 mm thick aluminum plate (material 1050, tempered H16) was immersed in a 5% aqueous sodium hydroxide solution maintained at 65 ° C, degreased for 1 minute, and then washed with water. This degreased aluminum plate was neutralized by immersing it in a 10% aqueous hydrochloric acid solution maintained at 25 ° C. for 1 minute, and then washed with water.

[0161] Then, the aluminum plate in a nitric acid aqueous solution of 0.3 wt%, 25 ° C, 60 seconds by alternating current under condition of current density of 1 OOA / dm ^2, after the electrolytic surface roughening The desmutting treatment was performed for 10 seconds in a 5% aqueous sodium hydroxide solution maintained at 60 ° C.

[0162] Desmutted roughened aluminum plate was anodized in 15% sulfuric acid solution at 25 ° C, current density 10A / dm ² , voltage 15V for 1 minute, and 1% The support 1 was prepared by subjecting it to hydrophilic treatment with polyvinyl phosphonic acid at 75 ° C.

 [0163] At this time, the centerline average roughness (Ra) of the surface was 0.665111.

[0164] Photosensitive layer coating solution 1 having the following composition was coated on the above support 1 with a wire bar so as to be 1.7 g / m ² when dried, dried at 80 ° C for 2 minutes, and then the following oxygen Apply the barrier layer coating solution 1 to 1.5 g / m ² when dried with a wire bar and dry at 75 ° C for 1.5 minutes for lithographic printing plate

 We got a fee;! ~ 8.

[0165] (Photosensitive layer coating solution 1)

 Polymer binder (methacrylic acid / methyl methacrylate copolymer = 14/86, mass average molecular weight = 36000) 44.0 parts

 Spectral sensitizer A 4.0 parts

 Iron arene complex: Irgacure 261 (Ciba Specialty Chemicals)

2. 9 copies Triazine compound (TAZ-107: Midori Chemical Co., Ltd.) 1. 5 parts

 Reaction generation of N—n butyljetanolamine (1 mol), 1,3-bis (1 isocyanatototo 1-methylethyl) benzene (2 mol), 2-hydroxyethyl methacrylate (2 mol) 33. 0 parts

 Polyethylene glycol # 200 dimetacrine HNK ester 3G, manufactured by Shin-Nakamura Chemical Co., Ltd., monomer SP: 9. 89) 11.0 parts

 Monofunctional monomer (monomer listed in Table 1 with added amount)

 Phthalocyanine pigment (MHI454, made by Gokoku Color Co., Ltd.) 5/4 parts

 2-t Butinole 6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4 ate (Sumilyzer GS: manufactured by Sumitomo 3M) 0.2 parts Siloxane-based surfactant (BYK337; manufactured by Big Chemi) 0. 9 parts Hindered amine light stabilizer (LS 770, Sankyo Lifetech Co., Ltd.) 0.1 part Fluorosurfactant (F178K, Dainippon Ink and Chemicals) 0.1 part Amamine (ANCAMIN K-54 (Product made by Air Products) 1. 4 parts Propylene Glyconore Mechinoleatere 820 parts

 (Oxygen barrier coating solution 1)

 Polybur alcohol (Celball 103: Celaneas) 79 · 0 parts

 Bullpyrrolidone / Butyl acetate copolymer (Rubitec VA64W: manufactured by BASF)

 20.0 copies

 Surfynol 465 (Air Products) 1. 0 parts

 900 parts of water

[Chemical 1] Awake HEAA ACMQ

 I. , To γ

 ο Ο

 0

HE A N1PAM

Spectral sensitizer A

[0167] <Evaluation of photosensitive lithographic printing plate material>

 << Sensitivity >>

 A 100% solid image is output while changing the exposure energy of the laser. According to the above image forming method, the density of each energy of the developed image is measured with a densitometer [D196: manufactured by GRE TAG].

[0168] The exposure energy at which the density began to drop from the saturated solid density of the photosensitive material was taken as the sensitivity.

 The amount of energy at which the saturated solid density X 0.9 was obtained was converted.

[0169] 《Under developability》

 The developer temperature was changed in steps of 2 ° C, development processing was performed, and the developability of the non-image area was evaluated.

 [0170] After development, the lower limit of the developing solution temperature at which printing and non-image areas were not smudged or ink entangled in the shadow areas was determined.

[0171] Printing conditions: A lithographic printing plate produced by exposing an image of 175 lines with an appropriate exposure amount, heat-treating at 105 ° C, and developing at each temperature, using a printing machine (DAIYA1F-1 manufactured by Mitsubishi Heavy Industries, Ltd.) Printed using coated paper, printing ink (Dainippon Ink Chemical Co., Ltd., soybean oil ink "Naturalis 100") and dampening water (Tokyo ink H liquid SG-51 concentration 1.5%) Imprint 10 The non-image area and shadow after 00 sheets were visually evaluated and compared with a printed material having a development temperature of 28 ° C. as a reference, and judged as good or bad.

[0172] <Press life>

Under the following printing conditions, an evaluation chart of 175 lines exposed at 80 ^ j / cm ² was printed, and the number of printed sheets from the start of printing until the reproduction halftone dot changed by 3% was evaluated as printing durability.

[0173] (Printing conditions)

 Printing machine: DAIYA1F— 1: Mitsubishi Heavy Industries

 Paper: Coated paper (Recycled pulp content 20%, manufactured by Hokuetsu Paper Co., Ltd.)

 Blanket: SR100 (manufactured by SRI Hybrid)

 Printing ink: Soybean oil ink Natyralis 100 (Y, M, C, K): Dainippon Ink & Chemicals

 Dampening solution: Liquid H SG-51 concentration 1.5%: manufactured by Tokyo Ink

 Printing speed: 4000 sheets / hour

 <Reproducibility of halftone dots during exposure>

 Under an environment of 23 ° C and 60%, each printing plate was exposed with 50% output at the appropriate exposure amount, preheated and developed after 1 hour, and processed immediately after exposure. The halftone dot reproducibility was compared. Halftone dot reproducibility was measured with CC DOT (X—Rite).

 [0174] The results of the various evaluations are summarized in Table 1.

[0175] [Table 1]

As is apparent from the results shown in Table 1, the lithographic printing plate material according to the present invention has a sensitivity, printing durability, developability, and latent image stability (the time-lapse network from exposure to heat treatment). (Variable resistance of point reproducibility)! /, Excellent! /, Power of S component.

Claims

The scope of the claims

 [1] In a photosensitive lithographic printing plate material having a photosensitive layer containing a polymerizable ethylenically unsaturated bond-containing compound, a polymerization initiator, a spectral sensitizer, and a polymer binder on a support, The photosensitive lithographic printing plate material, wherein the photosensitive layer contains a monofunctional monomer having a dipole moment of 2.3 to 6.0 D as a polymerizable ethylenically unsaturated bond-containing compound .

 [2] The photosensitive lithographic printing plate material of [1], wherein the monofunctional monomer is an acrylamide derivative.

3. The photosensitive lithographic printing plate material according to claim 2, wherein the acrylamide derivative is N-alkylacrylamide.

[4] The photosensitive layer contains, as a polymerizable ethylenically unsaturated bond-containing compound, a polyfunctional acrylate having an amide bond and a tertiary amino group in one molecule. Item 4. The photosensitive lithographic printing plate material according to any one of Items 1 to 3.