JP2007171755A - Photosensitive lithographic printing plate material, method for producing the same, and plate making method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To eliminate the effect of excess fluorescence from a spectral sensitizer without lowering sensitivity, and to achieve excellent resolution (linearity) and printing durability. <P>SOLUTION: A photosensitive lithographic printing plate material is provided, which has on a support a photopolymerizable photosensitive layer comprising a photosensitive composition containing at least (A) a monomer containing an addition polymerizable ethylenic double bond, (B) a photopolymerization initiator and (C) a polymer binder, wherein a support on which the photosensitive composition is applied is treated with a solution containing a dye having an absorption maximum at a wavelength of 400-500 nm at a step after anodizing the support and before applying the photosensitive composition. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a photosensitive lithographic printing plate material used in a so-called computer-to-plate (hereinafter referred to as CTP) system, and particularly suitable for exposure with a laser beam having a wavelength of 350 to 450 nm. The present invention relates to a lithographic printing plate material, a production method thereof and a plate making method.

  In recent years, digitization technology that electronically processes, stores, and outputs image information using a computer has become widespread, and in printing plate preparation technology for offset printing, directivity is determined according to digitized image information. A so-called CTP system that scans a high laser beam and records directly on a lithographic printing plate has been developed, and its practical application is progressing.

  Among these, in the field of printing that requires a relatively high printing durability, it is known to use a negative photosensitive lithographic printing plate material having a polymerization type photosensitive layer containing a polymerizable compound. (For example, refer to Patent Documents 1 and 2.)

  Light sources such as Ar laser (488 nm) and YD-YAG (532 nm) are known as light sources used for the polymerization type photosensitive layer, but the output is not sufficiently high in plate making using these light sources. Therefore, it is insufficient to increase the productivity of the plate making process, and the workability is insufficient from the viewpoint of the use of the safelight.

  On the other hand, in recent years, lasers capable of continuous transmission within the range of high-power and small-sized shortwave light (wavelength: 350 to 450 nm) have become readily available.

  In order to improve the above-described productivity and safelight properties, printing plate materials suitable for these short-wave lasers have been developed.

  As a printing plate material suitable for these short-wave lasers, for example, a printing plate material having a photosensitive layer suitable for a laser having a wavelength of 350 to 450 nm containing a specific carbonyl compound and a titanocene compound (see Patent Document 3), a specific spectral enhancement Printing plate material having a photosensitive layer suitable for a laser having a wavelength of 450 to 550 nm containing a sensitizer and a radical generator (see Patent Document 4), having a wavelength of 350 to 450 nm containing a specific styryl compound and a specific fluorescent whitening agent A printing plate material having a photosensitive layer suitable for a laser (see Patent Documents 5 and 6) is known.

However, spectral sensitizers used in these printing plate materials, particularly spectral sensitizers that absorb ultraviolet light in the wavelength region near 405 nm, may cause fluorescence emission at wavelengths longer than the absorption maximum wavelength. In many cases, it has been found that this fluorescent emission becomes scattered light and has a problem of reducing the resolution (linearity).
JP-A-1-105238 JP-A-2-127404 JP 2000-98605 A JP 2003-206307 A JP 2003-221517 A JP 2003-295426 A

  The present invention has been made in view of the above problems, and its purpose is to eliminate the influence of excessive fluorescence emission from the spectral sensitizer without lowering the sensitivity, and to be excellent in resolution (linearity) and printing durability. A photosensitive lithographic printing plate material, a production method thereof, and a plate making method using the same.

  The above-described problems of the present invention are solved by the following means.

  1. A photopolymerizable sensation comprising a photosensitive composition containing at least A) an addition-polymerizable ethylenic double bond-containing monomer, B) a photopolymerization initiator, and C) a polymer binder on a support. In a photosensitive lithographic printing plate material having an optical layer, the support absorbs at 400 nm or more and 500 nm or less after the anodizing treatment of the support on which the photosensitive composition is applied and before the application of the photosensitive composition. A photosensitive lithographic printing plate material which is treated with a solution containing a dye having a maximum wavelength.

  2. 2. The photosensitive lithographic printing plate material as described in 1 above, wherein the photosensitive composition contains at least one bisimidazole compound.

  3. 3. The photosensitive lithographic printing plate material as described in 1 or 2 above, wherein the photosensitive composition contains at least one iron arene complex compound.

  4). A photopolymerizable photosensitive composition comprising a photosensitive composition containing at least A) an ethylenic double bond-containing monomer capable of addition polymerization, B) a photopolymerization initiator, and C) a polymer binder on a support. In the method for producing a photosensitive lithographic printing plate material having a layer, in the step after the anodizing treatment of the support to which the photosensitive composition is applied and before the application of the photosensitive composition, the support is 400 nm or more and 500 nm or less. A method for producing a photosensitive lithographic printing plate material, comprising treating with a solution containing a dye having an absorption maximum wavelength.

  5. 4. A plate making method of a photosensitive lithographic printing plate material, wherein the photosensitive lithographic printing plate material according to any one of 1 to 3 is subjected to image exposure with a laser beam and developed with an alkaline developer.

  The constitution of the present invention provides a photosensitive lithographic printing plate material excellent in resolution (linearity) and printing durability by removing the influence of excessive fluorescence emission from the spectral sensitizer without lowering the sensitivity. A manufacturing method and a plate making method using the same can be provided.

  The photosensitive lithographic printing plate material of the present invention comprises, on a support, at least A) an addition-polymerizable ethylenic double bond-containing monomer, B) a photopolymerization initiator composition, and C) a polymer binder. In a photosensitive lithographic printing plate material having a photopolymerizable photosensitive layer containing the photosensitive composition, the anodizing treatment of the support to which the photosensitive composition is applied and before the photosensitive composition is applied. In the step, the support is treated with a solution containing a dye having an absorption maximum wavelength of 400 nm to 500 nm.

  Hereinafter, the present invention and its components will be described in detail.

(dye)
The dye according to the present invention may be any dye as long as the maximum absorption is in the range of 400 to 500 nm. Preferably, the dye represented by the following general formula [FD1] or general formula [FD2] improves the object effect of the present invention. Play.

In general formula [FD1], R ₁ is a carboxyl group, an alkyl group (preferably having 1 to 3 carbon atoms), a substituted alkyl group (preferably having 1 to 3 carbon atoms, and preferred substituents are a halogen atom, a hydroxy group, etc.), aryl Represents a group selected from a group (preferably a phenyl group), an alkoxycarbonyl group (the alkyl part is preferably having 1 to 3 carbon atoms) and an aryloxycarbonyl group (preferably a phenyloxycarbonyl group), and R ₂ represents a sulfonic acid group or Represents a group selected from an alkyl group substituted with a carboxyl group (preferably having 1 to 3 carbon atoms) and an aryl group substituted with a sulfonic acid group or a carboxyl group (preferably a phenyl group), R ₃ , R ₄ , R ₅ and R ₆ are a hydrogen atom, an alkyl group (preferably 1 to 3 carbon atoms) and substituted alkyl groups (preferably 1 to 3 carbon atoms Preferred substituents represents a group or atom selected from a halogen atom, a hydroxyl group).

  These dyes can be synthesized, for example, by the method described in Japanese Patent Publication No. 31-10578.

  Specific examples of the dye represented by the general formula [FD1] are listed below, but the present invention is not limited thereto.

R ₁ and R _{2 in} the general formula [FD2] are a carboxyl group, an alkyl group (preferably an alkyl group having 1 to 3 carbon atoms), and a substituted alkyl group (preferably an alkyl group having 1 to 3 carbon atoms). The group is selected from a halogen atom, a hydroxyl group, etc., an aryl group (preferably a phenyl group), an alkoxycarbonyl group (the alkyl part is preferably having 1 to 3 carbon atoms) and an aryloxycarbonyl group (preferably a phenyloxycarbonyl group). R ₃ and R ₄ are each an alkyl group substituted with a sulfonic acid group or a carboxyl group (preferably an alkyl group having 1 to 3 carbon atoms) and an aryl group substituted with a sulfonic acid group or a carboxyl group (preferably Represents a group selected from phenyl group).

  Specific examples of the dye represented by the general formula [FD2] are shown below, but the present invention is not limited thereto.

  In the treatment with the dye (adsorption on the surface) in the present invention, it is very effective and preferable that the dye is adsorbed onto the support after the anodizing step and before coating of the photosensitive layer. Before anodization, it is not preferable because it is detached from the aluminum surface during anodization. After the anodizing treatment, generally, water rinsing, hydrophilic treatment, water rinsing, drying, and photosensitive layer coating are performed. The dye adsorption treatment is most preferably before the hydrophilization treatment, the next is preferably the same as the hydrophilization treatment, and the next is after the hydrophilization treatment (in this case, rinsing is required). Although the dye solution may be applied or dipped before the photosensitive layer is applied, it is not preferable to dry without rinsing and apply the photosensitive layer, since the printing durability is reduced.

  The dye according to the present invention is preferably used as a solution by dissolving it in water or a hydrophilic organic solvent such as methanol or ethanol.

  The amount of the dye used is not uniform depending on the type of compound and the purpose, but the concentration of the dye solution is preferably 0.01% by mass or more and 5% by mass or less, more preferably 0.05% by mass or more and 1% by mass. % Or less.

  As a method of adsorbing the dye on the support, a method of immersing the support in the dye solution is preferable. The temperature of the dye solution at the time of immersion is 5 ° C. or higher and 80 ° C. or lower, preferably 10 ° C. or higher and 50 ° C. or lower. The immersion time is 0.1 second to 60 seconds, preferably 1 second to 30 seconds.

(Photosensitive composition)
Next, the compound etc. which are contained in the photosensitive composition concerning this invention are demonstrated.

A) Addition-polymerizable ethylenic double bond-containing monomer As one of the main components of the photosensitive composition contained in the photopolymerizable photosensitive layer according to the present invention (hereinafter also simply referred to as “photosensitive layer”). As such, an addition-polymerizable ethylenic double bond-containing monomer is used.

  Addition-polymerizable ethylenic double bond-containing monomers are general radical-polymerizable monomers, and many monomers having a plurality of addition-polymerizable ethylenic double bonds in the molecule generally used for UV curable resins. Functional monomers and polyfunctional oligomers can be used. The compound is not limited, but preferred examples include 2-ethylhexyl acrylate, 2-hydroxypropyl acrylate, glycerol acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, nonylphenoxyethyl acrylate, tetrahydrofurfuryloxyethyl acrylate, tetrahydro Furfuryloxyhexanolide acrylate, acrylate of ε-caprolactone adduct of 1,3-dioxane alcohol, monofunctional acrylic acid esters such as 1,3-dioxolane acrylate, or these acrylates as methacrylate, itaconate, crotonate, maleate Methacrylic acid, itaconic acid, crotonic acid, maleic acid ester such as ethylene glycol diamine Rate, triethylene glycol diacrylate, pentaerythritol diacrylate, hydroquinone diacrylate, resorcin diacrylate, hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate of hydroxypivalate, neo Diacrylate of pentyl glycol adipate, diacrylate of ε-caprolactone adduct of neopentyl glycol hydroxypivalate, 2- (2-hydroxy-1,1-dimethylethyl) -5-hydroxymethyl-5-ethyl-1,3 -Ε-caprolactone addition of dioxane diacrylate, tricyclodecane dimethylol acrylate, tricyclodecane dimethylol acrylate , Bifunctional acrylic esters such as diglycidyl ether diacrylate of 1,6-hexanediol, or methacrylic acid, itaconic acid, crotonic acid, maleic acid ester obtained by replacing these acrylates with methacrylate, itaconate, crotonate, maleate For example, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, trimethylolethane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, dipenta Ε-caprolactone adduct of erythritol hexaacrylate, pyrogallol triacryl Polyfunctional acrylic acid esters such as propionate / dipentaerythritol triacrylate, propionic acid / dipentaerythritol tetraacrylate, hydroxypivalylaldehyde-modified dimethylolpropane triacrylate, or these acrylates with methacrylate, itaconate, crotonate And methacrylic acid, itaconic acid, crotonic acid, maleic acid ester, etc., instead of maleate.

  Prepolymers can also be used as described above. Examples of the prepolymer include compounds as described below, and a prepolymer obtained by introducing acrylic acid or methacrylic acid into an oligomer having an appropriate molecular weight and imparting photopolymerizability can be preferably used. These prepolymers may be used alone or in combination of two or more, and may be used by mixing with the above-mentioned monomers and / or oligomers.

  Examples of prepolymers include adipic acid, trimellitic acid, maleic acid, phthalic acid, terephthalic acid, hymic acid, malonic acid, succinic acid, glutaric acid, itaconic acid, pyromellitic acid, fumaric acid, glutaric acid, pimelic acid, Polybasic acids such as sebacic acid, dodecanoic acid, tetrahydrophthalic acid, and ethylene glycol, propylene glycol, diethylene glycol, propylene oxide, 1,4-butanediol, triethylene glycol, tetraethylene glycol, polyethylene glycol, glycerin, trimethylol Polyester obtained by introducing (meth) acrylic acid into a polyester obtained by combining polyhydric alcohols such as propane, pentaerythritol, sorbitol, 1,6-hexanediol, 1,2,6-hexanetriol Chlorates such as bisphenol A, epichlorohydrin, (meth) acrylic acid, and epoxy acrylates in which (meth) acrylic acid is introduced into an epoxy resin such as phenol novolac, epichlorohydrin, (meth) acrylic acid, such as ethylene glycol, adipine Acid / tolylene diisocyanate / 2-hydroxyethyl acrylate, polyethylene glycol / tolylene diisocyanate / 2-hydroxyethyl acrylate, hydroxyethylphthalyl methacrylate / xylene diisocyanate, 1,2-polybutadiene glycol / tolylene diisocyanate / 2-hydroxyethyl acrylate , Trimethylolpropane, propylene glycol, tolylene diisocyanate, 2-hydroxyethyl acrylate In addition, urethane acrylates in which (meth) acrylic acid is introduced into urethane resin, for example, silicone resin acrylates such as polysiloxane acrylate, polysiloxane diisocyanate, 2-hydroxyethyl acrylate, etc., and (meth) acryloyl in oil-modified alkyd resins Examples thereof include prepolymers such as alkyd-modified acrylates having introduced groups and spirane resin acrylates.

  The photosensitive composition of the photopolymerizable photosensitive layer according to the present invention includes a phosphazene monomer, triethylene glycol, isocyanuric acid EO (ethylene oxide) -modified diacrylate, isocyanuric acid EO-modified triacrylate, dimethylol tricyclodecane diacrylate. A monomer such as trimethylolpropane acrylic acid benzoate, alkylene glycol type acrylic acid modified, urethane modified acrylate and the like, and an addition polymerizable oligomer and prepolymer having a structural unit formed from the monomer Can do.

  Furthermore, examples of the ethylenic monomer that can be used in combination with the present invention include phosphate ester compounds containing at least one (meth) acryloyl group. The compound is not particularly limited as long as it is a compound in which at least part of the hydroxyl group of phosphoric acid is esterified and has a (meth) acryloyl group.

  In addition, JP-A-58-212994, 61-6649, 62-46688, 62-48589, 62-173295, 62-187092, 63- 67189, JP-A-1-244891, and the like. Further, “11290 Chemical Products”, Chemical Industry Daily, p. 286-p. 294, “UV / EB Curing Handbook (raw material)”, Kobunshi Publishing Co., p. The compounds described in 11 to 65 can also be suitably used in the present invention. Of these, compounds having two or more acrylic groups or methacryl groups in the molecule are preferred in the present invention, and those having a molecular weight of 10,000 or less, more preferably 5,000 or less are preferred.

  In addition, the photosensitive composition of the photopolymerizable photosensitive layer according to the present invention includes an addition-polymerizable ethylenic double bond-containing monomer containing a tertiary amino group in the molecule, which is a tertiary amine monomer. It is preferable to use it. Although there is no particular limitation on the structure, a tertiary amine compound having a hydroxyl group modified with glycidyl methacrylate, methacrylic acid chloride, acrylic acid chloride or the like is preferably used. Specifically, polymerizable compounds described in JP-A-1-165613, JP-A-1-203413, and JP-A-1-197213 are preferably used.

  Furthermore, in the present invention, a tertiary amine monomer, a polyhydric alcohol containing a tertiary amino group in the molecule, a diisocyanate compound, and a compound containing an ethylenic double bond capable of addition polymerization with a hydroxyl group in the molecule are used. It is preferred to use a reaction product.

  Examples of the polyhydric alcohol having a tertiary amino group in the molecule include triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-tert. -Butyldiethanolamine, N, N-di (hydroxyethyl) aniline, N, N, N ', N'-tetra-2-hydroxypropylethylenediamine, p-tolyldiethanolamine, N, N, N', N'-tetra- 2-hydroxyethylethylenediamine, N, N-bis (2-hydroxypropyl) aniline, allyldiethanolamine, 3- (dimethylamino) -1,2-propanediol, 3-diethylamino-1,2-propanediol, N, N -Di (n-propyl) amino-2,3-propanediol, N, N-di (iso-propyl) amino-2,3-propanediol, 3- (N-methyl-N-benzylamino) -1, Although 2-propanediol etc. are mentioned, it is not limited to this.

  Examples of the diisocyanate compound include butane-1,4-diisocyanate, hexane-1,6-diisocyanate, 2-methylpentane-1,5-diisocyanate, octane-1,8-diisocyanate, 1,3-diisocyanate methyl-cyclohexanone. 2,2,4-trimethylhexane-1,6-diisocyanate, isophorone diisocyanate, 1,2-phenylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene-2,4-diisocyanate, tolylene- Examples include 2,5-diisocyanate, tolylene-2,6-diisocyanate, 1,3-di (isocyanatomethyl) benzene, 1,3-bis (1-isocyanato-1-methylethyl) benzene, and the like. Limited to Not.

  Examples of the compound containing an ethylenic double bond capable of addition polymerization with a hydroxyl group in the molecule include the following compounds MH-1 to MH-13, but are not limited thereto.

  Preferably, 2-hydroxyethyl methacrylate (MH-1), 2-hydroxyethyl acrylate (MH-2), 4-hydroxybutyl acrylate (MH-4), 2-hydroxypropylene-1,3-dimethacrylate (MH-) 7), 2-hydroxypropylene-1-methacrylate-3-acrylate (MH-8) and the like.

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

  Specific examples of reaction products of polyhydric alcohols containing tertiary amino groups in the molecule, diisocyanate compounds, and compounds containing ethylenic double bonds capable of addition polymerization with hydroxyl groups in the molecule are shown below. Shown in

M-1: reaction product of triethanolamine (1 mol), hexane-1,6-diisocyanate (3 mol), 2-hydroxyethyl methacrylate (3 mol) M-2: triethanolamine (1 mol), isophorone Reaction product of diisocyanate (3 mol) and 2-hydroxyethyl acrylate (3 mol) M-3: Nn-butyldiethanolamine (1 mol), 1,3-bis (1-isocyanato-1-methylethyl) Reaction product of benzene (2 mol) and 2-hydroxypropylene-1-methacrylate-3-acrylate (2 mol) M-4: Nn-butyldiethanolamine (1 mol), 1,3-di (isocyanatomethyl) ) Reaction of benzene (2 mol), 2-hydroxypropylene-1-methacrylate-3-acrylate (2 mol) Product M-5: Reaction product of N-methyldiethanolamine (1 mol), tolylene-2,4-diisocyanate (2 mol), 2-hydroxypropylene-1,3-dimethacrylate (2 mol) An acrylate or an alkyl acrylate described in JP-A-1-105238 and JP-A-2-127404 can be used.

  In the present invention, the addition-polymerizable ethylenic double bond-containing monomer is a compound represented by the following general formula (EM1) or general formula (EM2) (tertiary amine monomer according to the present invention). Is particularly preferred.

[Where Q ¹ is

Or -S-, R ⁴ represents an alkyl group, a hydroxyalkyl group or an aryl group, R ¹ and R ² each represent a hydrogen atom, an alkyl group or an alkoxyalkyl group, and R ³ represents a hydrogen atom, a methyl group or Represents an ethyl group, X ¹ represents a divalent group having 2 to 12 carbon atoms, and X ² represents a ² to 4 valent group, or

Z represents an alkyl group, an alkenyl group, an aryl group, a halogen atom, an alkoxyl group, or a heterocyclic group, p represents an integer of 1 to 4, q represents an integer of 1 to 3, and p + q ≦ 5. . D ¹ and D ² each represents a saturated hydrocarbon group having 1 to 5 carbon atoms, and E is a saturated hydrocarbon group having 2 to 12 carbon atoms, having 5 to 7 ring members. And a cycloaliphatic group containing up to two N, O or S atoms as ring members, an aromatic group having 6 to 12 carbon atoms, or a heterocyclic fragrance having a 5-membered or 6-membered ring Represents a group, a represents 0 or an integer of 1 to 4, b represents 0 or 1, c represents an integer of 1 to 3, m represents an integer of 2 to 4 depending on the valence of Q ^1. , N represents an integer of 1 to m, and all groups having the same definition can be the same or different from each other. ]
The compound represented by the general formula (EM1) will be described below.

In the general formula (EM1), examples of the alkyl group represented by R ⁴ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an iso-pentyl group, a 2-ethylhexyl group, an octyl group, and a decyl group. N-undecyl group, n-dodecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-docosadecyl group and the like. Examples of the hydroxyalkyl group represented by R ⁴ include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, and a hydroxypentyl group. Examples of the aryl group represented by R ⁴ include a phenyl group and a naphthyl group.

In the general formula (EM1), the alkyl group represented by R ¹ and R ² has the same meaning as the alkyl group represented by R ⁴ . Examples of the alkoxyalkyl group represented by R ¹ and R ² include a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, and a propoxyethyl group.

In the general formula (EM1), examples of the divalent group having 2 to 12 carbon atoms represented by X ¹ include a saturated hydrocarbon group and an arylene group. Examples of the saturated hydrocarbon group having 2 to 12 carbon atoms represented by X ¹ include an ethylene group, trimethylene group, tetramethylene group, propylene group, ethylethylene group, pentamethylene group, hexamethylene group, hepta Chain saturated hydrocarbon groups such as methylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, cyclohexylene group (for example, 1,6-cyclohexanediyl group, etc.), cyclopentylene, etc. And cyclic saturated hydrocarbon groups such as a group (for example, 1,5-cyclopentanediyl group). In the present invention, the saturated hydrocarbon group represented by X ¹ is preferably a cyclic saturated hydrocarbon group. Examples of the arylene group represented by X ¹ include a phenylene group and a naphthylene group.

In the general formula (EM1), the divalent group represented by X ² is a saturated hydrocarbon group or arylene group mentioned as a divalent group having 2 to 12 carbon atoms represented by X ^1. In addition, it is possible to use those in which up to 5 methylene groups in the saturated hydrocarbon group are substituted with oxygen atoms.

In formula (EM1), 3-valent group represented by X ² include those divalent group (saturated hydrocarbon group, an arylene group) represented by the above X ² is further one linking group attached For example, ethanetriyl group, propanetriyl group, butanetriyl group, pentanetriyl group, hexanetriyl group, heptanetriyl group, octanetriyl group, nonanetriyl group, decantriyl group, undecantriyl group, dodecantriyl group , Cyclohexanetriyl group, cyclopentanetriyl group, benzenetriyl group, naphthalenetriyl group and the like.

In formula (EM1), 4-valent group represented by X ^2, which has with a further one linking group to a trivalent group represented by the aforementioned X ^2, for example, pro Panjii alkylidene group, 1,3-propanediyl-2-ylidene group, butanediylidene group, pentanediylidene group, hexanediylidene group, heptanediylidene group, octanediylidene group, nonanediylidene group, decandiylidene group, undecandiylidene group, dodecandiylidene group , Cyclohexanediylidene group, cyclopentanediylidene group, benzenetetrayl group, naphthalenetetrayl group and the like.

In X ² of the general formula (EM1), Z represents an alkyl group, an alkenyl group, an aryl group, a halogen atom, an alkoxyl group, or a heterocyclic group. Examples of the alkyl group represented by Z include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an iso-pentyl group, a 2-ethylhexyl group, an octyl group, and a decyl group. Examples of the alkenyl group represented by Z include a 2-propenyl group, a 3-butenyl group, a 1-methyl-3-propenyl group, a 3-pentenyl group, a 1-methyl-3-butenyl group, and a 4-hexenyl group. Is mentioned. Examples of the aryl group represented by Z include a phenyl group, an m-chlorophenyl group, a p-tolyl group, and a naphthyl group. Examples of the halogen atom represented by Z include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkoxyl group represented by Z include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the heterocyclic group represented by Z include a pyridyl group, a pyrrolyl group, a 2-methylpyrrolyl group, an indolyl group, an imidazolyl group, a furyl group, a thiazolyl group, and a pyrimidinyl group.

In the general formula (EM1), examples of the saturated hydrocarbon group having 1 to 5 carbon atoms represented by D ¹ and D ² include a methylene group, a trimethylene group, a tetramethylene group, a propylene group, an ethylethylene group, Examples include a pentamethylene group and a cyclopentylene group.

In the general formula (EM1), a saturated hydrocarbon group having 2 to 12 carbon atoms represented by E is synonymous with a divalent group having 2 to 12 carbon atoms represented by X ^1. is there.

  In the general formula (EM1), as the cycloaliphatic group represented by E having 5 to 7 ring members and containing up to 2 N, O, or S atoms as ring members, for example, tetrahydrofuran Ring, pyrrolidine ring, pyrazoline ring, imidazoline ring, oxazoline ring, thiazoline ring, pyridazine ring, pyran ring, thiophene ring, isoxazoline ring, pyrroline ring, imidazoline ring, imidazolidine ring, pyrazolidine ring, pyrazoline ring, piperidine ring, piperazine A ring, a morpholine ring, and the like.

  In the general formula (EM1), examples of the aromatic group having 6 to 12 carbon atoms represented by E include a phenylene group and a naphthylene group.

  In the general formula (EM1), the heterocyclic ring of the heterocyclic aromatic group having a 5-membered or 6-membered ring represented by E includes a furan ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxazole ring, a thiazole ring, 1,2,3-oxadiazole ring, 1,2,3-triazole ring, 1,2,4-triazole ring, 1,3,4-thiadiazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, Examples thereof include s-triazine ring, benzofuran ring, indole ring, benzothiophene ring, benzimidazole ring, benzothiazole ring, purine ring, quinoline ring and isoquinoline ring.

  Here, each substituent represented by the general formula (EM1) described above may further have a substituent.

In the general formula (EM1), Q ¹ is preferably> N—, X ¹ has an aromatic ring, and more preferably X ¹ is derived from tolylene diisocyanate in specific examples of the following compounds 4-12 Have a structure such as ˜4-15, and more preferably, X ¹ has a structure such as 4-16 to 4-20 derived from tetramethylxylene diisocyanate.

  The compound represented by the general formula (EM1) can be synthesized with reference to a method well known to those skilled in the art, for example, a method described in Japanese Patent No. 2509288.

  Hereinafter, although the specific example of a compound represented by general formula (EM1) is given, this invention is not limited to these.

  Next, the compound represented by the following general formula (EM2) will be described.

[Where Q ² is

R ⁸ represents an alkyl group, a hydroxyalkyl group or an aryl group, R ⁵ and R ⁶ each represent a hydrogen atom, an alkyl group or an alkoxyalkyl group, and R ⁷ represents a hydrogen atom, a methyl group or an ethyl group. , D ³ and D ⁴ each represent a saturated hydrocarbon group having 1 to 5 carbon atoms, G is a saturated hydrocarbon group having 2 to 12 carbon atoms, and has 5 to 7 ring members And a cyclic aliphatic group containing up to 2 N, O or S atoms as ring members, an aromatic group having 6 to 12 carbon atoms, or a heterocyclic aromatic group having 5 to 6 ring members D and e represent an integer of 1 to 4, g represents an integer of 2 to 4 depending on the valence of Q ² , f represents an integer of 1 to g, and all groups having the same definition are mutually It can be the same or different. ]
In the general formula (EM2), R ⁸ may be different from each other when (g−f) is 2 or more. Compounds in which g and f are the same value are preferred. When R ⁸ is an alkyl group or a hydroxyalkyl group, the number of carbon atoms is preferably 2 to 8, and more preferably 2 to 4. When R ⁸ is an aryl group, it is preferably a single ring or two rings, more preferably a single ring, and may be substituted with an alkyl group, alkoxyalkyl group or halogen atom having up to 5 carbon atoms. If R ⁵ and R ⁶ is an alkyl group or an alkoxyalkyl group, the carbon number 1 to 5 are preferred. R ⁷ is preferably a methyl group.

D ³ and D ⁴ may be the same or different, and preferably form a 6-membered saturated heterocyclic ring with two nitrogen atoms.

  When G is a saturated hydrocarbon group, it preferably has 2 to 6 carbon atoms. When G is an aromatic group, a phenylene group is preferred. When G is a cyclic aliphatic group, a cyclohexylene group is preferred. In the case of an aromatic group, a 5- to 6-membered ring containing a nitrogen atom or a sulfur atom is preferable.

In order to obtain the compound represented by the general formula (EM2), when Q ² is> N- and f and g have the same value, glycidyl acrylate or alkyl acrylate is reacted with hydroxyalkylamine. Other compounds can be obtained in the same manner.

  Specific examples of the compound represented by the general formula (EM2) of the present invention are shown below.

  The addition amount of the addition-polymerizable ethylenic double bond-containing monomer according to the present invention is preferably 30 to 70% by mass, more preferably 40 to 60% by mass of the nonvolatile component of the photopolymerizable photosensitive layer.

B) Photopolymerization initiator The photopolymerization initiator according to the present invention has a function of initiating a polymerization reaction of a compound that can be polymerized by image exposure. Various polymerization initiators that are commonly used can be used.

  Specific examples of usable polymerization initiators include compounds capable of generating radicals described in JP-A-2002-537419, JP-A-2001-175006, JP-A-2002-278057, JP-A-2003-5363. In addition to the polymerization initiators described in JP-A-2003-76010, onium salts having two or more cation moieties in one molecule, and N-nitrosamine-based compounds described in JP-A-2001-133966. Compounds, compounds that generate radicals by heat described in JP-A No. 2001-343742, compounds that generate acids or radicals by heat described in JP-A No. 2002-6482, borate compounds described in JP-A No. 2002-116539, Compounds that generate acid or radical by heat described in JP-A-2002-148790 A photo- or thermal polymerization initiator having a polymerizable unsaturated group described in JP-A No. 2002-207293, an onium salt having a divalent or higher anion as a counter ion described in JP-A No. 2002-268217, No. 328465 Specific structure sulfonyl sulfone compound, Japanese Patent Application Laid-Open No. 2002-341519, a compound that generates radicals by heat, Japanese Patent Application Laid-Open No. 59-219307, Iron arene complex compound, Japanese Patent Application Laid-Open No. 2003-295426 Compounds such as the hexaarylbisimidazole described can also be used if necessary.

  As the polymerization initiator according to the present invention, among the above various polymerization initiators, a biimidazole compound and an iron arene complex compound are particularly preferable. It is also preferable to include a titanocene compound or a polyhalogen compound.

<Biimidazole compound>
The biimidazole compound according to the present invention is a derivative of biimidazole, and examples thereof include compounds described in JP-A No. 2003-295426.

  In the present invention, it is preferable to contain a hexaarylbiimidazole (HABI, triaryl-imidazole dimer) compound as the biimidazole compound.

  Processes for the production of HABIs are described in DE 1,470,154 and their use in photopolymerizable compositions is described in EP 24,629, EP 107,792, US 4,410,621, EP 215,453 and DE 3, 211 and 312.

  Preferred derivatives are, for example, 2,4,5,2 ′, 4 ′, 5′-hexaphenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4,5,4 ′, 5′-tetraphenylbiimidazole. Imidazole, 2,2'-bis (2-bromophenyl) -4,5,4 ', 5'-tetraphenylbiimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,5,4' , 5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,5,4 ', 5'-tetrakis (3-methoxyphenyl) biimidazole, 2,2'-bis (2- Chlorophenyl) -4,5,4 ', 5'-tetrakis (3,4,5-trimethoxyphenyl) -biimidazole, 2,5,2', 5'-tetrakis (2-chlorophenyl) -4,4 ' -Bis (3,4-dimethyl) Xylphenyl) biimidazole, 2,2'-bis (2,6-dichlorophenyl) -4,5,4 ', 5'-tetraphenylbiimidazole, 2,2'-bis (2-nitrophenyl) -4,5 , 4 ', 5'-tetraphenylbiimidazole, 2,2'-di-o-tolyl-4,5,4', 5'-tetraphenylbiimidazole, 2,2'-bis (2-ethoxyphenyl) -4,5,4 ', 5'-tetraphenylbiimidazole and 2,2'-bis (2,6-difluorophenyl) -4,5,4', 5'-tetraphenylbiimidazole.

  The amount of HABI is typically in the range of 0.01 to 30% by weight, preferably 0.5 to 20% by weight, based on the total weight of the non-volatile components of the photosensitive composition.

<Iron arene complex compound>
Next, the iron arene complex compound contained in the photopolymerization initiator composition of the present invention will be described.

  Examples of the iron arene complex compound include compounds described in JP-A No. 59-219307, and are typically compounds represented by the following general formula (F).

In the formula, R ₁₁ and R ₁₂ are the same or different groups, C _{1 to} C ₁₂ alkyl group, C _{2 to} C ₁₂ alkynyl group, C _{1 to} C ₈ alkoxy group, cyano group, alkylthio group, a phenoxy group, C ₂ -C ₆ monocarboxylic acid and ester groups, alkanoyl groups of C ₂ -C _5, an ammonium salt, a pyridinium group, a nitro group, an alkylsulfinyl group, alkylsulfonyl group, selected from a sulfamoyl group halogen atom R ₁₂ may form a condensed polycyclic compound with a benzene ring. X represents BF ₄ , PF ₆ , AsF ₆ , SbF ₆ , FeCl ₄ , SnCl ₆ , SbCl ₆ , BiCl ₆ . m represents a positive integer of 1 to 4, and n represents a positive integer of 1 to 5.

Specific examples of the iron arene complex compound represented by formula (F) are shown below.
Fe-1: (η6-benzene) (η5-cyclopentadienyl) iron (2) hexafluorophosphate Fe-2: (η6-toluene) (η5-cyclopentadienyl) iron (2) hexafluorophosphate Fe— 3: (η6-cumene) (η5-cyclopentadienyl) iron (2) hexafluorophosphate Fe-4: (η6-benzene) (η5-cyclopentadienyl) iron (2) hexafluoroarsenate Fe-5 : (Η6-benzene) (η5-cyclopentadienyl) iron (2) tetrafluoroporate Fe-6: (η6-naphthalene) (η5-cyclopentadienyl) iron (2) hexafluorophosphate Fe-7: ( η6-anthracene) (η5-cyclopentadienyl) iron (2) hexafluorophosphate Fe-8: (η6-pyrene) Lopentagenyl) iron (2) hexafluorophosphate Fe-9: (η6-benzene) (η5-cyanocyclopentadienyl) iron (2) hexafluorophosphate Fe-10: (η6-toluene) (η5-acetylcyclopentazinini ) Iron (2) Hexafluorophosphate Fe-11: (η6-cumene) (η5-cyclopentadienyl) Iron (2) Tetrafluoroborate Fe-12: (η6-benzene) (η5-carboethoxycyclohexadienyl) ) Iron (2) hexafluorophosphate Fe-13: (η6-benzene) (η5-1,3-dichlorocyclohexadienyl) iron (2) hexafluorophosphate Fe-14: (η6-cyanobenzene) (η5- Cyclohexadienyl) iron (2) hexafluorophosphate Fe-15: (η6 Acetophenone) (η5-cyclohexadienyl) iron (2) hexafluorophosphate Fe-16: (η6-methylbenzoate) (η5-cyclopentadienyl) iron (2) hexafluorophosphate Fe-17: (η6-benzenesulfone Amido) (η5-cyclopentadienyl) iron (2) tetrafluoroborate Fe-18: (η6-benzamide) (η5-cyclopentadienyl) iron (2) hexafluorophosphate Fe-19: (η6-cyanobenzene ) (Η5-cyanocyclopentadienyl) iron (2) hexafluorophosphate FE-20: (η6-chloronaphthalene) (η5-cyclopentadienyl) iron (2) hexafluorophosphate Fe-21: (η6-anthracene) ) (Η5-cyanocyclopentadienyl) iron (2) Xafluorophosphate Fe-22: (η6-chlorobenzene) (η5-cyclopentadienyl) iron (2) Hexafluorophosphate Fe-23: (η6-chlorobenzene) (η5-cyclopentadienyl) iron (2) Tetrafluoroborate These compounds are described in Dokl. Akd. It can be synthesized by the method described in Nauk SSSR 149 615 (1963).

  The addition amount of the iron arene complex compound is preferably 0.1 to 15% by mass, more preferably 1 to 15% by mass, and still more preferably 1.5 to 10% by mass per nonvolatile component of the photopolymerizable photosensitive layer.

<Titanocene compound>
The photopolymerizable photosensitive layer according to the present invention preferably contains a titanocene compound as a photopolymerization initiator composition. Examples of titanocene compounds include compounds described in JP-A-63-41483 and JP-A-2-291. More preferred specific examples include bis (cyclopentadienyl) -Ti-di-chloride, bis (Cyclopentadienyl) -Ti-bis-phenyl, bis (cyclopentadienyl) -Ti-bis-2,3,4,5,6-pentafluorophenyl, bis (cyclopentadienyl) -Ti-bis -2,3,5,6-tetrafluorophenyl, bis (cyclopentadienyl) -Ti-bis-2,4,6-trifluorophenyl, bis (cyclopentadienyl) -Ti-bis-2,6 -Difluorophenyl, bis (cyclopentadienyl) -Ti-bis-2,4-difluorophenyl, bis (methylcyclopentadienyl) -Ti-bis- , 3,4,5,6-pentafluorophenyl, bis (methylcyclopentadienyl) -Ti-bis-2,3,5,6-tetrafluorophenyl, bis (methylcyclopentadienyl) -Ti-bis -2,6-difluorophenyl (IRUGACURE 727L: manufactured by Ciba Specialty Chemicals), bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyridin-1-yl) phenyl) titanium (IRUGACURE 784: Ciba Specialty Chemicals), bis (cyclopentadienyl) -bis (2,4,6-trifluoro-3- (pyridin-1-yl) phenyl) titanium bis (cyclopentadienyl) -bis (2, 4,6-trifluoro-3- (2-5-dimethylpy-1-yl) phenyl) titanium and the like It is below.

<Polyhalide>
The photopolymerizable photosensitive layer according to the present invention preferably contains a polyhalogen compound as a photopolymerization initiator composition. Examples of the polyhalogen compound include compounds represented by the following general formulas (PX1) to (PX3).

[Wherein, Z ₁ and Z ₂ each independently represent a halogen atom, X represents a hydrogen atom or an electron-withdrawing group, Y ₁ represents a —CO— group or a —SO ₂ — group, and Q ₃ represents an arylene. L represents a linking group, W represents a carboxyl group or a salt thereof, a sulfo group or a salt thereof, a phosphoric acid group or a salt thereof, a hydroxyl group, a quaternary ammonium group, or a polyethyleneoxy group. To express. r represents 0 or 1; ]

[Wherein, Q ₄ represents an alkyl group, an aryl group or a heterocyclic group, and X ₁ and X ₂ each represent a halogen atom. Z represents a hydrogen atom or an electron-withdrawing group. Y represents —C (═O) —, —SO— or —SO ₂ —. s represents 0 or 1. ]

[Wherein, Q ₅ represents an alkyl group, an aryl group or a heterocyclic group, and X ₄ , X ₅ and X ₆ each represents a hydrogen atom or a halogen atom, but at least one of X ₄ , X ₅ and X ₆ Represents a halogen atom. t represents an integer of 0 to 4, and u represents an integer of 1 to 5. ]
Typical specific examples of the compounds represented by the general formulas (PX1) to (PX3) are listed below, but the present invention is not limited thereto.

  The polyhalogen compound contained in the photopolymerization initiator composition of the present invention is preferably a polyhaloacetyl compound, and more preferably a trihaloacetylamide compound. Examples of the polyhaloacetyl compound include a compound represented by the following general formula (PX4) or more preferably a compound represented by the following general formula (PX5).

Formula (PX4) R ¹¹ —C (X ¹⁰ ) ₂ — (C═O) —R ¹²
In the formula, X ¹⁰ represents a chlorine atom or a bromine atom. R ¹¹ represents a hydrogen atom, a chlorine atom, a bromine atom, an alkyl group, an aryl group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group or a cyano group. R ¹² represents a monovalent substituent. R ¹¹ and R ¹² may be bonded to form a ring.

Formula (PX5) C (X ¹¹ ) ₃ — (C═O) —Y ¹⁰ —R ¹³
In the formula, X ¹¹ represents a chlorine atom or a bromine atom. R ¹³ represents a monovalent substituent. Y ¹⁰ represents —O— or —NR ¹⁴ —. R ¹⁴ represents a hydrogen atom or an alkyl group. R ¹³ and R ¹⁴ may combine to form a ring.

  Representative specific examples (BR1 to BR76) of the compound represented by the general formula (PX4) are listed below, but the present invention is not limited thereto.

  Furthermore, as the polyhaloacetyl compound, a compound represented by the general formula (PX5) is preferably used. Preferable specific examples of the compound represented by the general formula (PX5) are the compounds of BR2 to BR47 and BR67 to BR76.

  In the polyhalogen compounds represented by the general formulas (PX1) to (PX5), polybromine compounds are more preferable.

  Examples of polyhalogen compounds preferably used in the present invention include trihalomethyltriazine compounds. For example, Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), for example, 2-phenyl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -S-triazine, 2- (2 ', 4'-dichlorophenyl) -4,6-bis (trichloromethyl) -S-triazine, 2,4,6-tris (trichloromethyl) -S-triazine, 2-methyl-4, 6-bis (trichloromethyl) -S-triazine, 2-n-nonyl-4,6-bis (trichloromethyl) -S-triazine, 2- (α, α, β-trichloroethyl) -4, - bis (trichloromethyl) -S- triazine. In addition, compounds described in British Patent 1388492, for example, 2-styryl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-methylstyryl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl) -4-amino-6-trichloromethyl-S-triazine, etc. And compounds described in JP-A-53-133428, such as 2- (4-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- (4-ethoxy-naphtho) 1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl] -4,6-bis-trick Rumethyl-S-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- (acenaphtho-5-yl) -4,6-bis Examples thereof include -trichloromethyl-S-triazine and the compounds described in German Patent 3337024. F.F. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), such as 2-methyl-4,6-bis (tribromomethyl) -S-triazine, 2,4,6-tris (tribromomethyl) -S-triazine, 2, 4,6-tris (dibromomethyl) -S-triazine, 2-amino-4-methyl-6-tribromomethyl-S-triazine, 2-methoxy-4-methyl-6-trichloromethyl-S-triazine, etc. be able to.

(Spectral sensitizer)
When laser light is used as the light source, a spectral sensitizer is preferably added to the photosensitive layer. It is preferable to use a spectral sensitizer having an absorption maximum wavelength near the wavelength of the light source. The spectral sensitizer according to the present invention increases the sensitivity of the photopolymerization initiator to image exposure.

  The spectral sensitizer according to the present invention is preferably a compound that absorbs light having a wavelength in the emission wavelength region of the recording light source. Specifically, a compound having an absorption maximum from 350 nm to 450 nm is preferable, and a compound having an absorption maximum from 350 to 410 nm is more preferable.

  Next, a photopolymerization initiator that is preferably used in the present invention has a maximum absorption at 350 nm or more and 450 nm or less where a preferable effect can be obtained by using in combination with a biimidazole compound, an iron arene complex compound, a polyhalogen compound, or the like. Spectral sensitizers include xanthenes, acridines, coumarins, and barbiturates, and more preferably spectral sensitizers that can be represented by the following general formula (SS1).

In the general formula (SS1), A ¹ and A ² each represent a carbon atom or a hetero atom. Q ¹ represents a nonmetallic atomic group necessary for forming a heterocyclic ring together with A ¹ , A ² and the carbon atoms adjacent to them. R ¹ and R ² each represent a hydrogen atom, an alkyl group or an aryl group. R ¹ and R ² may be bonded to each other to form a ring. X ¹ and X ² each represent a cyano group or a substituted carbonyl group, and X ¹ and X ² may be bonded to each other to form a ring. n is 0, 1 or 2.

Specific examples of the spectral sensitizer represented by the general formula (SS1) are shown below, but the present invention is not limited thereto. In the following, (indicated by Q ¹⁾ ring completed by Q ^1, X ¹ and X ² and are also intended to indicate a combination of bonded carbon divalent group and n, in these R ¹ = R ² = H.

  Examples of other spectral sensitizers represented by the general formula (SS1) include compounds described in JP-A-9-328505.

  The spectral sensitizer having an absorption maximum at 350 nm or more and 450 nm or less that can be used in combination with one of the iron arene complex compound and the polyhalogen compound according to the present invention can be used in combination. It is a spectral sensitizer that can be represented by (SS2) or general formula (SS3).

In the general formula (SS2), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ are hydrogen, alkyl A group, an alkoxy group, an aryl group, a cyano group, a carboxyl group, an alkyloxycarbonyl group, and Z ¹ is an aryl group, a heterocyclic group, or —COR ¹⁶ (R ¹⁶ is an alkyl group, an alkoxy group, an aryl group, An aryloxy group or a heterocyclic group).

  Specific examples of the spectral sensitizer represented by the general formula (SS2) are shown below, but the present invention is not limited thereto.

In the general formula (SS3), R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ are hydrogen, alkyl group, alkoxy group, aryl group, cyano group, carboxyl A group, an alkyloxycarbonyl group, and Z ² represents an aryl group, a heterocyclic group, or —COR ²⁶ (R ²⁶ represents an alkyl group, an alkoxy group, an aryl group, an aryloxy group, or a heterocyclic group). Show.

  Specific examples of the spectral sensitizer represented by the general formula (SS3) are shown below, but the present invention is not limited thereto.

  Other spectral sensitizers having an absorption maximum at 350 nm or more and 450 nm or less that can obtain a preferable effect by further use in combination with any one of the polyhalogen compounds according to the present invention and the iron arene complex compound, Examples thereof include xanthene dyes such as rose bengal, phloxine, erythrosine, eosin, fluorescein, coumarin dyes, and anthracene dyes. Specific examples of the spectral sensitizer are shown below, but the present invention is not limited thereto.

  A spectral sensitizer having an absorption maximum at 350 nm or more and 600 nm or less that can be used in combination with any of the polyhalogen compounds according to the present invention and those used in combination with the iron arene complex compound includes cyanine dyes. Carbocyanine dyes, hemicyanine dyes, rhodamine dyes, and azamethine dyes. Specific examples of the spectral sensitizer are shown below, but the present invention is not limited thereto.

  Next, any of the polyhalogen compounds according to the present invention, or any of the polyhalogen compounds according to the present invention and the iron arene complex compound can be further used together to obtain a preferable effect. Examples of spectral sensitizers having a maximum include JP-A No. 2000-98605, JP-A No. 2000-147663, JP-A No. 2000-206690, JP-A No. 2000-258910, JP-A No. 2001-42524, Spectral sensitizers described in JP-A No. 2001-100412 and the like are preferable. More preferably, a compound represented by the following general formula (SS4) is preferable.

In the formula, R ¹⁴ has a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent or a substituent. Represents an optionally substituted heterocyclic group. R ¹⁵ and R ¹⁶ represent a substituent that can be linked to form a ring. X ¹¹ and X ¹² each independently represent —C (R ¹⁷ R ¹⁸ ) —, —O—, —S—, or —N (R ¹⁹ ) —. R ¹⁷ , R ¹⁸ and R ¹⁹ are each independently a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an aryl which may have a substituent. Represents a heterocyclic group which may have a group or a substituent.

Examples of the alkyl group optionally having a substituent represented by R ¹⁴ include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, an isopropyl group, and an isobutyl group. Group, isopentyl group, tert-butyl group, 2-ethylhexyl group and the like. Examples of the alkenyl group which may have a substituent represented by R ¹⁴ include a vinyl group and a 2-propenyl group. , 3-butenyl group, 1-methyl-3-propenyl group, 3-pentenyl group, 1-methyl-3-butenyl group, 4-hexenyl group and the like, and has a substituent represented by R ^14. Examples of the aryl group that may be used include a phenyl group and a naphthyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group. The heterocyclic group which may have a substituent represented by R ^14, for example, a pyrrole ring, an imidazole ring, a pyrazole ring, an oxazole ring, a thiazole ring, an oxadiazole ring, a thiadiazole ring, benzimidazole ring, Heterocyclic groups derived from 5-membered or 6-membered heterocycles such as pyridine ring, furan ring, thiophene ring, chroman ring, coumarin ring, pyrrolidine ring, piperidine ring, morpholine ring, sulfolane ring, tetrahydrofuran ring and tetrahydropyran ring Can be mentioned.

In addition, an alkyl group which may have a substituent represented by R ¹⁷ , R ¹⁸ and R ¹⁹ , an alkenyl group which may have a substituent, an aryl group which may have a substituent, or Examples of the heterocyclic group which may have a substituent include the same groups as those described for R ¹⁴ above.

  An example of the spectral sensitizer represented by the general formula (SS4) is shown below, but the present invention is not limited thereto.

  The spectral sensitizer represented by the general formula (SS4) can be synthesized by a person skilled in the art according to a conventionally known method.

  In the present invention, in addition to the above-described spectral sensitizers, spectral sensitizers having different chemical structures may be used in combination. Specific examples of spectral sensitizers that can be used in combination include optical brighteners described in JP2003-295426A, spectral sensitizers described in JP2003-211901, and general formulas described in JP2003-21895A. A compound having a structure represented by (I), a compound having a structure represented by general formula (I) in JP-A-2003-21894, and a spectral sensitizer having a specific structure in JP-A-2002-351072 Spectral sensitizer having a specific structure of JP-A No. 2002-351071, SPECTRAL SENSITIZER having a specific structure (pyrrolopyrrole ring) of JP-A No. 2002-351655, Spectral sensitization of JP-A No. 2002-268239 Sensitizer, spectral sensitizer of JP 2002-268238 A, spectral sensitizer of JP 2002-268204 A, general formula of JP 2002-221790 A A compound having a structure represented by I), a compound having a structure represented by general formula (I) in JP-A No. 2002-202598, a carbazole-based spectral sensitizer in JP-A No. 2001-042524, No. 2000-309724, No. 2000-258910, No. 2000-206690, Naphtho [1,8-b, c] furan-5-one derivative, Examples thereof include merocyanine dyes disclosed in Japanese Utility Model Laid-Open No. 2000-147763, and carbonyl compounds disclosed in Japanese Patent Application Laid-Open No. 2000-098605.

  In addition to the above exemplified spectral sensitizers, examples of preferable spectral sensitizers that can be used in combination include, for example, cyanine, merocyanine, porphyrin, spiro compound, ferrocene, fluorene, fulgide, imidazole, perylene, phenazine, Phenothiazine, acridine, azo compound, diphenylmethane, triphenylmethane, triphenylamine, coumarin derivative, quinacridone, indigo, styryl, pyrylium compound, pyromethene compound, pyrazolotriazole compound, benzothiazole compound, barbituric acid derivative, thiobarbitur An acid derivative, a keto alcohol borate complex, etc. can also be mentioned.

  The absorption maximum of the spectral sensitizer is dissolved in acetonitrile and the visible light spectrum is measured at room temperature. Spectral sensitizers that are insoluble in acetonitrile may be measured by dissolving in alcohols, 2-butanone, water, or the like.

  In the present invention, as a method for adding the spectral sensitizer, water or an appropriate solvent such as an organic solvent can be selected and dissolved in them, and examples of the organic solvent include methanol, ethanol, and propanol. Alcohols such as butanol; ketones such as acetone, methyl ethyl ketone, cyclohexanone; aromatic hydrocarbons such as benzene, toluene, xylene; glycols such as ethylene glycol, propylene glycol, hexylene glycol; ethyl cellosolve, butyl cellosolve, ethyl Glycol ethers such as carbitol, butyl carbitol, diethyl cellosolve and diethyl carbitol; N-methylpyrrolidone, dimethylformamide and the like can be mentioned, and these can be used alone or in combination of two or more.

  The addition amount of the spectral sensitizer according to the present invention in the photosensitive layer is arbitrary, but is preferably in the range of 0.1 to 20% by mass with respect to the total mass of the photosensitive layer. Furthermore, it is preferably 0.8 to 15% by mass. More specifically, when the composition of the photosensitive lithographic printing plate material is used, an addition amount in which the absorbance of the reflection spectrum using an integrating sphere at the laser wavelength to be used is in the range of 0.2 to 2.0 is preferable. More preferably, the addition amount is an absorbance of 0.3 to 1.2.

  These spectral sensitizers may be used alone or in combination of two or more.

  The mixing ratio of the photopolymerization initiator and the spectral sensitizer is preferably in the range of 1: 100 to 100: 1 in terms of molar ratio.

C) Polymer Binder The polymer binder according to the present invention has a function of holding each component contained in the photopolymerizable photosensitive layer.

  Examples of the polymer binder used in the photopolymerizable photosensitive layer according to the present invention include, for example, acrylic polymers, polyvinyl butyral resins, polyurethane resins, polyamide resins, polyester resins, epoxy resins, phenol resins, polycarbonate resins, Polyvinyl butyral resin, polyvinyl formal resin, shellac, other natural resins, and the like can be used. Two or more of these may be used in combination.

  Each of the above polymer binders is preferably a vinyl copolymer obtained by copolymerization of an acrylic monomer. Further, as a copolymer composition of the polymer binder, (a) a carboxyl group-containing monomer, (b ) It is preferably a copolymer of methacrylic acid alkyl ester or acrylic acid alkyl ester.

  Specific examples of the carboxyl group-containing monomer include α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride and the like. In addition, carboxylic acids such as phthalic acid and 2-hydroxymethacrylate half ester are also preferable.

  Specific examples of the alkyl methacrylate and the alkyl acrylate include, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, methacrylic acid. Nonyl acid, decyl methacrylate, undecyl methacrylate, dodecyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, nonyl acrylate In addition to unsubstituted alkyl esters such as decyl acrylate, undecyl acrylate and dodecyl acrylate, cyclic alkyl ethers such as cyclohexyl methacrylate and cyclohexyl acrylate Tellurium, benzyl methacrylate, 2-chloroethyl methacrylate, N, N-dimethylaminoethyl methacrylate, glycidyl methacrylate, benzyl acrylate, 2-chloroethyl acrylate, N, N-dimethylaminoethyl acrylate, glycidyl acrylate, etc. Examples thereof include substituted alkyl esters.

  Furthermore, in the polymer binder according to the present invention, monomers described in the following (1) to (14) can be used as other copolymerization monomers.

  (1) Monomers having an aromatic hydroxyl group, such as o- (or p-, m-) hydroxystyrene, o- (or p-, m-) hydroxyphenyl acrylate, and the like.

  (2) Monomers having an aliphatic hydroxyl group, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N-methylol acrylamide, N-methylol methacrylamide, 4-hydroxybutyl methacrylate, 5-hydroxypentyl acrylate, 5-hydroxypentyl Methacrylate, 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, N- (2-hydroxyethyl) acrylamide, N- (2-hydroxyethyl) methacrylamide, hydroxyethyl vinyl ether and the like.

  (3) A monomer having an aminosulfonyl group, such as m- (or p-) aminosulfonylphenyl methacrylate, m- (or p-) aminosulfonylphenyl acrylate, N- (p-aminosulfonylphenyl) methacrylamide, N- ( p-aminosulfonylphenyl) acrylamide and the like.

  (4) Monomers having a sulfonamide group, such as N- (p-toluenesulfonyl) acrylamide, N- (p-toluenesulfonyl) methacrylamide and the like.

  (5) Acrylamide or methacrylamides such as acrylamide, methacrylamide, N-ethylacrylamide, N-hexylacrylamide, N-cyclohexylacrylamide, N-phenylacrylamide, N- (4-nitrophenyl) acrylamide, N-ethyl-N -Phenylacrylamide, N- (4-hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) methacrylamide and the like.

  (6) Monomers containing fluorinated alkyl groups such as trifluoroethyl acrylate, trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, hexafluoropropyl methacrylate, octafluoropentyl acrylate, octafluoropentyl methacrylate, heptadecafluorodecyl methacrylate, N -Butyl-N- (2-acryloxyethyl) heptadecafluorooctylsulfonamide and the like.

  (7) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, phenyl vinyl ether and the like.

  (8) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate, vinyl benzoate and the like.

  (9) Styrenes such as styrene, methyl styrene, chloromethyl styrene and the like.

  (10) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.

  (11) Olefins such as ethylene, propylene, i-butylene, butadiene, isoprene and the like.

  (12) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine and the like.

  (13) Monomers having a cyano group, such as acrylonitrile, methacrylonitrile, 2-pentenenitrile, 2-methyl-3-butenenitrile, 2-cyanoethyl acrylate, o- (or m-, p-) cyanostyrene.

  (14) A monomer having an amino group, such as N, N-diethylaminoethyl methacrylate, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, polybutadiene urethane acrylate, N, N-dimethylaminopropyl acrylamide, N , N-dimethylacrylamide, acryloylmorpholine, Ni-propylacrylamide, N, N-diethylacrylamide and the like.

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

  In addition, a double bond-containing vinyl copolymer obtained by addition reaction of a compound having a (meth) acryloyl group and an epoxy group in the molecule to a carboxyl group present in the molecule of the vinyl copolymer is also provided. It is preferable as a polymer binder. Specific examples of the compound containing both a double bond and an epoxy group in the molecule include glycidyl acrylate, glycidyl methacrylate, and an epoxy group-containing double compound described in JP-A No. 11-271969.

  These copolymers preferably have a mass average molecular weight of 1 to 200,000 as measured by gel permeation chromatography (GPC), but are not limited to this range.

  The polymer binder may include any other polymer binder such as polyvinyl butyral resin, polyurethane resin, polyamide resin, polyester resin, epoxy resin, novolac resin, natural resin, etc., if necessary. You may use together with a copolymer.

  The content of the polymer binder in the composition for coating the photopolymerizable photosensitive layer is preferably 10 to 90% by mass, more preferably 15 to 70% by mass, and 20 to 60% by mass. It is particularly preferable from the viewpoint of sensitivity.

  Furthermore, the vinyl copolymer obtained by copolymerization of acrylic monomers is preferably 50 to 100% by mass, and more preferably 80 to 100% by mass in the polymer binder.

  The acid value of the polymer contained in the polymer binder according to the present invention is preferably used in the range of 10 to 150, more preferably in the range of 30 to 120, and in the range of 50 to 90. From the viewpoint of balancing the polarity of the entire photosensitive layer, it is particularly preferable, and this can prevent aggregation of the pigment in the photosensitive layer coating solution.

(Chain transfer agent)
A chain transfer agent is a compound added to a polymerization reaction system for the purpose of adjusting the degree of polymerization of a polymer, etc., and has a function of changing the type of chain transfer body in the course of a chain polymerization reaction. .

  The chain transfer agent according to the present invention is preferably a radical chain transfer agent as described in EP 107792 in order to promote or control the polymerization reaction of the polymerizable compound according to the present invention. Specific examples of preferable radical chain transfer agents include mercapto compounds. In particular, the photosensitive layer preferably contains a heteroaromatic mercapto compound or a mercapto derivative compound represented by the following general formula [RCT].

General formula [RCT]
Ar-SM
In the formula, M is a hydrogen atom or an alkali metal atom, and Ar is a heteroaromatic ring or a condensed heteroaromatic ring having at least one atom selected from nitrogen, sulfur, oxygen, selenium or tellurium atom. Heteroaromatic rings include It is preferably a quinoline or quinazoline ring. In addition, a heteroaromatic mercapto compound having a heteroaromatic ring having a chemical structure different from that of the exemplified compound may be contained in the photosensitive layer as the chain transfer agent according to the present invention.

  Hereinafter, various additives that can be added to the photosensitive composition in the present invention, a support as a photosensitive lithographic printing plate, a protective layer, application of the photosensitive composition to the support, and the photosensitive lithographic printing plate The image recording method and the like will be described sequentially.

(Various additives)
In the present invention, the photopolymerizable photosensitive layer containing the photosensitive composition does not require an ethylenic double bond monomer that can be polymerized during the production or storage of the photosensitive lithographic printing plate, in addition to the components described above. In order to prevent proper polymerization, it is desirable to add a polymerization inhibitor. Suitable polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol) 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxylamine cerium salt, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5) -Methylbenzyl) -4-methylphenyl acrylate and the like.

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

  Moreover, a coloring agent can also be used and a conventionally well-known thing can be used conveniently as a coloring agent including a commercially available thing. Examples include those described in the revised new edition “Pigment Handbook”, edited by Japan Pigment Technology Association (Seikodo Shinkosha), Color Index Handbook, and the like.

  Examples of the pigment include black pigment, yellow pigment, red pigment, brown pigment, purple pigment, blue pigment, green pigment, fluorescent pigment, and metal powder pigment. Specifically, inorganic pigments (titanium dioxide, carbon black, graphite, zinc oxide, Prussian blue, cadmium sulfide, iron oxide, and lead, zinc, barium and calcium chromates) and organic pigments (azo-based, thioindigo) , Anthraquinone, anthanthrone, and triphendioxazine pigments, vat dye pigments, phthalocyanine pigments and derivatives thereof, quinacridone pigments, and the like.

  Among these, it is preferable to select and use a pigment having substantially no absorption in the absorption wavelength region of the spectral sensitizer corresponding to the exposure laser to be used. In this case, an integrating sphere at the laser wavelength to be used is used. It is preferable that the reflection absorption of the used pigment is 0.05 or less. Moreover, as an addition amount of a pigment, 0.1-10 mass% is preferable with respect to solid content of the said composition, More preferably, it is 0.2-5 mass%.

  When an argon laser (488 nm) or SHG-YAG laser (532 nm) is used as an exposure light source, purple pigments and blue pigments are used from the viewpoints of pigment absorption in the photosensitive wavelength region and visible image properties after development. It is preferable to use it. Such as, for example, cobalt blue, cerulean blue, alkali blue lake, phonatone blue 6G, Victoria blue lake, metal-free phthalocyanine blue, phthalocyanine blue first sky blue, indanthrene blue, indico, dioxane violet, iso Violanthrone Violet, Indanthrone Blue, Indanthrone BC and the like can be mentioned. Among these, phthalocyanine blue and dioxane violet are more preferable.

  Moreover, the said composition can contain surfactant as a coating property improving agent in the range which does not impair the performance of this invention. Of these, fluorine-based surfactants are preferred.

  In order to improve the physical properties of the cured film, additives such as an inorganic filler, a plasticizer 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.

  Moreover, as a solvent used when preparing the photosensitive composition of the photopolymerizable photosensitive layer according to the present invention, for example, in the case of alcohol: polyhydric alcohol derivatives, sec-butanol, isobutanol, n-hexanol, Benzyl alcohol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,5-pentanediol, ethers: propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ketones, aldehydes: diacetone Preferable examples include alcohol, cyclohexanone, methylcyclohexanone, and esters: ethyl lactate, butyl lactate, diethyl oxalate, methyl benzoate and the like.

(Protective layer: oxygen barrier layer)
A protective layer is preferably provided on the upper side of the photopolymerizable photosensitive layer according to the present invention. The protective layer (oxygen barrier layer) preferably has high solubility in a developer described later (generally an alkaline aqueous solution), and specific examples include polyvinyl alcohol and polyvinyl pyrrolidone. Polyvinyl alcohol has an effect of suppressing permeation of oxygen, and polyvinyl pyrrolidone has an effect of ensuring adhesion with an adjacent photosensitive layer.

  In addition to the above two polymers, polysaccharides, polyethylene glycol, gelatin, glue, casein, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, hydroxyethyl starch, gum arabic, sucrose octaacetate, ammonium alginate, sodium alginate as required Water-soluble polymers such as polyvinylamine, polyethylene oxide, polystyrene sulfonic acid, polyacrylic acid, and water-soluble polyamide can also be used in combination.

  In the photosensitive lithographic printing plate of the present invention, the peeling force between the photosensitive layer and the protective layer is preferably 35 mN / mm or more, more preferably 50 mN / mm or more, and further preferably 75 mN / mm or more. Preferred examples of the protective layer composition include those described in Japanese Patent Application No. 8-161645.

  In the present invention, the peeling force is obtained by applying an adhesive tape having a predetermined width on the protective layer and having a sufficiently large adhesive force, and peeling it together 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 determined by measuring the force.

  The protective layer can further contain a surfactant, a matting agent and the like as required. The 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 alcohols such as methanol, ethanol, i-propanol.

  The thickness of the protective layer is preferably from 0.1 to 5.0 μm, particularly preferably from 0.5 to 3.0 μm.

(Support)
As the support according to the present invention, an aluminum support having a hydrophilic surface is used. In this case, pure aluminum or an aluminum alloy may be used.

  Various aluminum alloys can be used as the support, and for example, alloys of metals such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, nickel, titanium, sodium, iron, and aluminum are used. .

  Prior to roughening (graining treatment), the support is preferably subjected to a degreasing treatment in order to remove the rolling oil on the surface. As the degreasing treatment, a degreasing treatment using a solvent such as trichlene or thinner, an emulsion degreasing treatment using an emulsion such as kesilon or triethanol, or the like is used. In addition, an alkaline aqueous solution such as caustic soda can 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 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 and desmutted. It is preferable to perform the treatment.

  As a roughening method used in the present invention, roughening is performed by electrolysis, but before that, roughening can be performed by, for example, a mechanical method.

The mechanical roughening method used is not particularly limited, but a brush polishing method and a honing polishing method are preferable. The roughening by the brush polishing method is, for example, by rotating a rotating brush using a bristle having a diameter of 0.2 to 0.8 mm, and for example, volcanic ash particles having a particle size of 10 to 100 μm on water. While supplying the uniformly dispersed slurry, the brush can be pressed. The roughening by honing polishing is performed by, for example, uniformly dispersing volcanic ash particles having a particle size of 10 to 100 μm in water, injecting pressure from a nozzle, and causing the surface to collide obliquely with the support surface. Can do. Further, for example, abrasive particles having a particle size of 10 to 100 μm are applied to the support surface so as to be present at a density of 2.5 × 10 ³ to 10 × 10 ³ particles / cm ² at intervals of 100 to 200 μm. Roughening can also be performed by laminating the sheets and applying a pressure to transfer the rough surface pattern of the sheet.

After the surface is roughened by the mechanical surface roughening method, it is preferable to immerse in an aqueous solution of acid or alkali in order to remove the abrasive that has digged into the surface of the support, formed aluminum scraps, and the like. 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 and potassium hydroxide. Among these, it is preferable to use an aqueous alkali solution such as sodium hydroxide. The dissolution amount of aluminum in the support surface, 0.5 to 5 g / m ² is preferred. After the immersion treatment with an alkaline aqueous solution, it is preferable to carry out a neutralization treatment by immersion in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid or a mixed acid thereof.

In the present invention, as a roughening method, roughening by electrolysis is performed. In this method, the surface is electrochemically roughened in an acidic electrolytic solution, and the acidic electrolytic solution has an effective value of 30 A in a hydrochloric acid or nitric acid solution having a concentration of 0.4% by mass to 2.8% by mass. / dm ² or more 100A / dm ² or less at a current density of 10 seconds to 120 seconds, performing electrolytic graining. The concentration of hydrochloric acid or nitric acid is more preferably 1% by mass or more and 2.3% by mass or less. Current density is more preferably 30A / dm ² or more 80A / dm ² or less, further preferably 40A / dm ² or more 75A / dm ² or less.

The temperature at which the electrolytic surface-roughening method is performed is not particularly limited, but is preferably in the range of 5 ° C. to 80 ° C., more preferably in the range of 10 ° C. to 60 ° C. The applied voltage is not particularly limited, but is preferably performed by applying a voltage in the range of 1 to 50 volts, and more preferably in the range of 10 to 30 volts. Quantity of electricity is not particularly limited, it is preferable to use a range of 5000 C / dm ^2, still preferably selected from the range of 100~2000c / dm ^2.

  If necessary, nitrate, chloride, amines, aldehydes, phosphoric acid, chromic acid, boric acid, acetic acid, oxalic acid, and the like can be added to the electrolytic solution.

After the surface is roughened by the electrolytic surface roughening method, it is preferably immersed in an acid or alkaline aqueous solution 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 and potassium hydroxide. Among these, it is preferable to use an alkaline aqueous solution. The dissolution amount of aluminum in the support surface, 0.5 to 5 g / 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.

Following the electrolytic surface roughening treatment, an anodic oxidation treatment can be performed. There is no restriction | limiting in particular in the method of the anodizing process which can be used in this invention, A well-known method can be used. By performing the anodizing treatment, an oxide film is formed on the support. For the anodizing treatment, a method of electrolyzing an aqueous solution containing sulfuric acid and / or phosphoric acid at a concentration of 10 to 50% as an electrolytic solution at a current density of 1 to 10 A / dm ² is preferably used. A method of electrolysis at a high current density in sulfuric acid described in Japanese Patent No. 1,412,768, a method of electrolysis using phosphoric acid described in Japanese Patent No. 3,511,661, chromic acid, Examples thereof include a method using a solution containing one or more oxalic acid, malonic acid and the like. The formed anodic oxidation coating amount is suitably 1 to 50 mg / dm ² , preferably 10 to 40 mg / dm ² . The anodized coating amount is obtained by, for example, immersing an aluminum plate in a chromic phosphate solution (85% phosphoric acid solution: 35 ml, prepared by dissolving 20 g of chromium (IV) oxide in 1 L of water) to dissolve the oxide film, It is obtained from mass change measurement before and after dissolution of the coating on the plate.

  In the present invention, the support is preferably treated with a sodium silicate solution having a temperature of 20 ° C. or more and 50 ° C. or less after the anodizing treatment. The temperature is preferably 20 ° C. or higher and 50 ° C. or lower, and more preferably 20 ° C. or higher and 45 ° C. or lower. If it is less than 20 ° C., it may become dirty and recovery may be worsened. Further, if it is higher than 50 ° C., the printing durability may be deteriorated. The concentration of sodium silicate is not particularly limited, but is preferably 0.01% or more and 35% or less, and more preferably 0.1% or more and 5% or less.

  In the present invention, the support is preferably treated with a polyvinylphosphonic acid solution having a temperature of 20 ° C. or more and 70 ° C. or less after the anodizing treatment. The temperature is preferably 20 ° C. or higher and 70 ° C. or lower, and more preferably 30 ° C. or higher and 65 ° C. or lower. If it is less than 20 ° C., it may become dirty and recovery may be worsened. On the other hand, if it is higher than 70 ° C., the printing durability may be deteriorated. The concentration of the polyvinylphosphonic acid solution is not particularly limited, but is preferably 0.01% or more and 35% or less, and more preferably 0.1% or more and 5% or less.

(Application)
The prepared photosensitive composition (photopolymerizable 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. Examples of coating methods for 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 coater method. I can list them.

  If the drying temperature of the photosensitive layer is low, sufficient printing durability cannot be obtained. If the drying temperature is too high, not only marangoni is produced but also fogging of a non-image area is caused. The preferable drying temperature range is preferably 60 to 160 ° C, more preferably 80 to 140 ° C, and particularly preferably 90 to 120 ° C.

(Image recording method)
As a light source for recording an image on the photosensitive lithographic printing plate material of the present invention, laser light having an emission wavelength of 350 to 450 nm is preferably used.

  As a light source for exposing the photosensitive lithographic printing plate of the present invention, for example, a He-Cd laser (441 nm), a combination of Cr: LiSAF and SHG crystal (430 nm) as a solid laser, KNbO3 as a semiconductor laser system, ring resonance Examples include a vessel (430 nm), AlGaInN (350 nm to 450 nm), an AlGaInN semiconductor laser (commercially available InGaN-based semiconductor laser 400 to 410 nm), and the like.

  Laser exposure is suitable for direct writing without using a mask material because light exposure can be performed in the form of a beam according to image data.

  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.

  Laser scanning methods include cylindrical outer surface scanning, cylindrical inner surface scanning, and planar scanning. In the cylindrical outer surface scanning, laser exposure is performed while rotating a drum around which the recording material is wound, and the rotation of the drum is the main scanning and the movement of the laser light 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 a main scanning is performed in the circumferential direction by rotating a part or all of the optical system. Sub scanning is performed in the axial direction by linearly moving all of them in parallel with the drum axis. In plane scanning, a laser beam main scan is performed by combining a polygon mirror, a galvanometer mirror, and an fθ lens, and a sub-scan is performed by moving a recording medium. Cylindrical outer surface scanning and cylindrical inner surface scanning are easier to increase the accuracy of the optical system and are suitable for high-density recording.

In the present invention, image exposure is preferably 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 10-300 mJ / cm < ² >. For this energy measurement, for example, a laser power meter PDGDO-3W manufactured by OphirOptics can be used.

(Preheat)
In the present invention, it is preferable to heat-treat the photosensitive lithographic printing plate material after exposing the image to the lithographic printing plate and before or during development. By performing the heat treatment in this manner, the adhesion between the photosensitive layer and the support is improved, and the effects of the invention according to the present invention can be improved.

  The preheating according to the present invention is performed by, for example, a preheating roller that heats a photosensitive lithographic printing plate carried during development processing to a predetermined temperature range before development in an automatic developing apparatus that develops photosensitive lithographic printing plate material. The method of heating can be mentioned. For example, the preheat roller is composed of a pair of rollers including at least one roller having heating means therein, and the roller having the heating means is a hollow made of a metal having high thermal conductivity (for example, aluminum, iron, etc.). It is possible to use a pipe in which a nichrome wire or the like is embedded as a heating element and the outer surface of the metal pipe is covered with a plastic sheet such as polyethylene, polystyrene, or Teflon (registered trademark). For details of such a preheat roller, reference can be made to JP-A No. 64-80962.

  The preheating in the present invention is preferably performed at 70 to 180 ° C. for about 3 to 120 seconds.

(Developer)
The exposed portion of the photosensitive layer subjected to image exposure is cured. By developing this with an alkaline developer, the unexposed areas are removed and image formation becomes possible. As such a developer, a conventionally known alkaline aqueous solution can be used. For example, sodium silicate, potassium, ammonium; dibasic sodium phosphate, potassium, ammonium; sodium bicarbonate, potassium, ammonium; sodium carbonate, potassium, ammonium; sodium bicarbonate, potassium, ammonium An alkali developer using an inorganic alkaline agent such as sodium borate, potassium, ammonium; sodium hydroxide, potassium, ammonium and lithium;

  Also, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, mono-i-propylamine, di-i-propylamine, tri-i-propylamine, butylamine, monoethanolamine, diethanolamine, triethanolamine, Organic alkali agents such as mono-i-propanolamine, di-i-propanolamine, ethyleneimine, ethylenediamine, and pyridine can also be used.

  These alkali agents are used alone or in combination of two or more. In addition, an organic solvent such as an anionic surfactant, an amphoteric surfactant or alcohol can be added to the developer as necessary.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, the aspect of this invention is not limited to this. In the examples, “parts” represents “parts by mass” unless otherwise specified.

Example 1
<< Polymer binder: Synthesis of acrylic copolymer 1 >>
In a three-necked flask under a nitrogen stream, 30 parts of methacrylic acid, 50 parts of methyl methacrylate, 20 parts of ethyl methacrylate, 500 parts of isopropyl alcohol and 3 parts of α, α′-azobisisobutyronitrile are placed in a nitrogen stream. The reaction was carried out in an oil bath at 0 ° C. for 6 hours. Then, after refluxing at the boiling point of isopropyl alcohol for 1 hour, 3 parts of triethylammonium chloride and 25 parts of glycidyl methacrylate were added and reacted for 3 hours to obtain an acrylic copolymer 1. The mass average molecular weight measured using GPC was about 35,000, and the glass transition temperature (Tg) measured using DSC (differential thermal analysis) was about 85 ° C.

[Production of support]
Using a JIS A 1050 aluminum plate having a thickness of 0.30 mm and a width of 1030 mm, the treatment was continuously performed as follows.

(A) The aluminum plate was etched by spraying at a caustic soda concentration of 2.6 mass%, an aluminum ion concentration of 6.5 mass%, and a temperature of 70 ° C. to dissolve the aluminum plate by 0.3 g / m ² . Thereafter, washing with water was performed by spraying.

  (B) A desmut treatment was performed by spraying with a 1% by mass aqueous solution of nitric acid having a temperature of 30 ° C. (including 0.5% by mass of aluminum ions), and then washed with water by spraying.

(C) An electrochemical surface roughening treatment was continuously performed using an alternating voltage of 60 Hz. The electrolytic solution at this time contains 0.5% by mass of aluminum ions and 0.007% by mass of acetic acid. The temperature was 21 ° C. The AC power source was subjected to electrochemical surface roughening treatment using a sine wave alternating current having a time TP of 2 msec until the current value reached a peak from zero, using a carbon electrode as a counter electrode. The current density was an effective value of 50 A / dm ² and the energization amount was 900 C / dm ² . Then, water washing by spraying was performed.

  (D) A desmut treatment was performed for 10 seconds with a phosphoric acid concentration 20 mass% aqueous solution (containing 0.5 mass% of aluminum ions) at a temperature of 60 ° C., followed by washing with water by spraying.

(E) An anodizing apparatus of an existing two-stage feed electrolytic treatment method (first and second electrolysis unit length 6 m, first feed unit length 3 m, second feed unit length 3 m, first and second feed electrode lengths 2.4 m each ) Was used to perform anodization at a sulfuric acid concentration of 170 g / liter (containing 0.5 mass% of aluminum ions) at a temperature of 38 ° C. Thereafter, washing with water was performed by spraying. At this time, in the anodizing device, the current from the power source flows to the first power supply electrode provided in the first power supply unit, flows to the plate-like aluminum via the electrolytic solution, An oxide film is formed on the surface, passes through the electrolytic electrode provided in the first power feeding portion, and returns to the power source. On the other hand, the current from the power source flows to the second power feeding electrode provided in the second power feeding portion, similarly flows to the plate-like aluminum via the electrolytic solution, and an oxide film is formed on the surface of the plate-like aluminum by the second electrolysis portion. Although the amount of electricity fed from the power source to the first feeding unit and the amount of electricity fed from the power source to the second feeding unit are the same, the feeding current density on the oxide film surface in the second feeding unit is about It was 25 A / dm ² . In the 2nd electric power feeding part, it came to feed from the oxide film surface of 1.35 g / m < ² >. The final oxide film amount was 2.7 g / m ² .

  The treatment after anodization is shown in the table. Thereafter, it was washed with spray water and dried with an infrared heater.

  At this time, the center line average roughness (Ra) of the surface was 0.55 μm.

(Preparation of photosensitive lithographic printing plate)
On the above support, a photopolymerizable photosensitive layer coating solution having the following composition was applied with a wire bar so that it would be 1.5 g / m ² when dried, and dried at 95 ° C. for 1.5 minutes. Got. Further, on the photopolymerized photosensitive layer coating sample, an oxygen barrier layer coating solution having the following composition was coated with a wire bar so that the drying rate was 1.8 g / m ² , and dried at 75 ° C. for 1 minute. A photosensitive lithographic printing plate sample having an oxygen blocking layer was prepared.

(Photopolymerizable photosensitive layer coating solution 1)
Ethylene double bond-containing monomer (1-17) 31.0 parts Ethylene double bond-containing monomer (NK ester 4G: Shin-Nakamura Chemical Co., Ltd.) 14.0 parts Spectral sensitizer (dye) -1) 3 parts Polymerization initiator: (Titanocene Ti-1 listed in Table 1) 4.0 parts Acrylic copolymer 1 45.0 parts Phthalocyanine pigment (MHI454: manufactured by Gokoku Dye Co., Ltd.) 6.0 parts Fluorine interface Activator (FC-4430; manufactured by Sumitomo 3M) 0.5 parts Dowanol PM 900 parts (oxygen barrier coating liquid)
Polyvinyl alcohol (GL-05: manufactured by Nippon Synthetic Chemical Co., Ltd.) 79 parts Polyvinylpyrrolidone (PVP K-30: manufactured by IPS Japan Co., Ltd.) 10 parts Polyethyleneimine (Lupazole WF: manufactured by BASF Corp.) 5 parts Cationic modified polyvinyl alcohol (Kuraray) C polymer: Kuraray Co., Ltd.) 5 parts Surfactant (Surfinol 465: Nissin Chemical Industry Co., Ltd.) 0.5 part Water 900 parts <Developer composition>
A Potassium silicate 8.0 mass%
New Coal B-13SN (Nippon Emulsifier Co., Ltd.) 2.0% by mass
Pronon # 204 (Nippon Yushi Co., Ltd.) 1.0% by mass
Caustic potash pH = 12.9 added amount

<< Evaluation of photosensitive lithographic printing plate >>
(Evaluation of sensitivity)
Using a plate setter (manufactured by ECRM) equipped with a 405 nm light source, exposure was performed at 2400 dpi (dpi represents the number of dots per inch, that is, 2.54 cm). The exposure energy (μJ / cm ² ) that reproduces 3% of the point corresponding to 3% of the output without linearity correction. The halftone dot output portion was photographed with a 1000 × optical microscope, and the area of the image portion was calculated as%.

(Evaluation of printing durability)
The exposure was performed at 2400 dpi using a plate setter (manufactured by ECRM) equipped with a light source of 405 nm under the condition that the exposure energy on the printing plate was 50 μJ / cm ² . After exposure, a preheating part for heat-treating the photosensitive lithographic printing plate at 105 ° C. for 10 seconds, a pre-water washing part for removing the oxygen blocking layer before development, a development part filled with a developer of the above composition, and a developer adhered to the plate surface Developed with a CTP automatic developing machine (PHW32-V: manufactured by Technigraph) equipped with a washing section for removing water and a gum solution for protecting the image area (GW-3: a product obtained by diluting a product made by Mitsubishi Chemical) Processing was carried out to obtain a lithographic printing plate.

  The prepared lithographic printing plate was coated with a printing press (DAIYA1F-1 manufactured by Mitsubishi Heavy Industries, Ltd.), printing ink (Toyo King High Echo M Red manufactured by Toyo Ink Co., Ltd.) and dampening water (Tokyo Ink Co., Ltd.). ) Manufactured H liquid SG-51 density 1.5%), and after continuous printing 600 sheets, wipe the plate surface with a cleaner to reduce the number of prints where the highlight part is thin and the shadow part is entangled. It was used as an index of printing force. One printing durability refers to the operation of wiping with a cleaner after 600 continuous printings. The more it is, the better. The cleaner uses an Ultra Plate Cleaner (Distributor: Dainichi Seika).

(Evaluation of linearity)
A halftone dot image of 175 lines at 2400 dpi was drawn from 0% to 100% in 1% increments without linearity correction. When exposure was performed with an exposure energy reproducing 3%, a halftone dot output image that should be 70% was taken with a 1000 × optical microscope, and the percentage of the image area calculated was defined as linearity. The closer to 70%, the better.

(Example 2)
A sample was prepared and evaluated in the same manner as in Example 1 except that the initiator was changed to the initiator shown in Table 2.

(Example 3)
A sample was prepared and evaluated in the same manner as in Example 1 except that the initiator shown in Table 3 was changed.

  The evaluation results of Examples 1 to 3 are summarized in Table 1, Table 2, and Table 3, respectively.

  As is apparent from the results shown in Tables 1 to 3, it can be seen that the sensitivity of the lithographic printing plate material according to the present invention is almost maintained and the printing durability and linearity are excellent. That is, it is possible to provide a photosensitive lithographic printing plate material excellent in resolution (linearity) and printing durability by removing the influence of excessive fluorescence emission from the spectral sensitizer without lowering the sensitivity, its production method, and it It can be seen that a plate making method using can be provided.

Claims (5)

A photopolymerizable sensation comprising a photosensitive composition containing at least A) an addition-polymerizable ethylenic double bond-containing monomer, B) a photopolymerization initiator, and C) a polymer binder on a support. In a photosensitive lithographic printing plate material having an optical layer, the support absorbs at 400 nm or more and 500 nm or less after the anodizing treatment of the support on which the photosensitive composition is applied and before the application of the photosensitive composition. A photosensitive lithographic printing plate material which is treated with a solution containing a dye having a maximum wavelength. The photosensitive lithographic printing plate material according to claim 1, wherein the photosensitive composition contains at least one bisimidazole compound. The photosensitive lithographic printing plate material according to claim 1, wherein the photosensitive composition contains at least one iron arene complex compound. A photopolymerizable photosensitive composition comprising a photosensitive composition containing at least A) an ethylenic double bond-containing monomer capable of addition polymerization, B) a photopolymerization initiator, and C) a polymer binder on a support. In the method for producing a photosensitive lithographic printing plate material having a layer, in the step after the anodizing treatment of the support to which the photosensitive composition is applied and before the application of the photosensitive composition, the support is 400 nm or more and 500 nm or less. A method for producing a photosensitive lithographic printing plate material, comprising treating with a solution containing a dye having an absorption maximum wavelength. 4. A method for making a photosensitive lithographic printing plate material according to claim 1, wherein the photosensitive lithographic printing plate material according to claim 1 is image-exposed with a laser beam and developed with an alkaline developer.