JP2005345978A - Method for manufacturing photosensitive planographic printing plate and usage method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a photosensitive planographic printing plate, having high workability and realizing printing with superior plate wear, contamination recovering property, printability and dot quality of a print, and to provide its usage method. <P>SOLUTION: The method for manufacturing a photosensitive planographic printing plate which has a photosensitive layer, containing (A) a polymerizable ethylenically unsaturated bond-containing compound and (B) a photopolymerization initiator on a support body and which is exposed to laser light of 350 to 500 nm emission wavelength includes at least a coating step, a drying step, a cutting step, and inspecting/selecting step. Any one of the steps in the coating step, drying step, cutting step and inspecting/selecting step is carried out under illumination by a light-emitting diode lamp having 530 to 620 nm maximum emission wavelength. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing a photosensitive lithographic printing plate suitable for a computer-to-plate system (hereinafter referred to as CTP) using a laser, and a method for using the same, and in particular, a method for producing a photosensitive lithographic printing plate having a photopolymerizable photosensitive layer, and Regarding usage.

  In recent years, CTP recording digital image data directly on a photosensitive printing plate with a laser light source has been developed and is being put to practical use in the technology for producing printing plates for offset printing.

  Photosensitive lithographic printing plates for CTP for recording digital data with a laser, for example, a photopolymerization system containing titanocene which is a polymerization initiator described in JP-A-9-80750 and JP-A-10-101719 and a specific dye Those having a photosensitive layer are known. However, since these photosensitive lithographic printing plates use a relatively long-wavelength visible light source as a light source, it is necessary to perform plate-making work for preparing the printing plate under a safe light of a dark red light. There was a demand for being able to handle under a brighter yellow light (lighting room).

  Further, a CTP plate material for recording digital data with a laser is required to have high sensitivity in order to shorten the recording time.

  Then, a high-power and small-sized blue-violet laser having a wavelength of 390 to 430 nm can be easily obtained, and a bright room has been developed by developing a photosensitive lithographic printing plate suitable for this laser wavelength.

  In printing areas where printing durability is required, printing plate materials having a photopolymerizable photosensitive layer have been proposed as printing plate materials corresponding to the laser (for example, Patent Documents 1, 2, 3, 4). 5).

However, when these printing plate materials are manufactured and used for printing, they can be performed under a yellow light, but the above-described manufacturing and use workability, printing durability, and stain recovery are still possible. In terms of properties, printing latitude, and dot quality of printed matter.
JP 2000-35673 A JP 2000-98605 A JP 2000-147663 A JP 2002-202598 A JP 2003-21901 A

  An object of the present invention is to provide a method for producing and using a photosensitive lithographic printing plate that has high workability and gives printing excellent in printing durability, stain recovery, printability, and print quality.

  The above object of the present invention is achieved by the following means.

(Claim 1)
Photosensitivity having a photosensitive layer containing (A) a polymerizable, ethylenically unsaturated bond-containing compound and (B) a photopolymerization initiator on a support and exposed to a laser beam having an emission wavelength of 350 nm to 500 nm. A method for producing a lithographic printing plate, comprising at least a coating step, a drying step, a cutting step, and an inspection / sorting step, and any step of the coating step, the drying step, the cutting step, and the inspection / sorting step Is carried out under a light emitting diode lamp having an emission wavelength maximum at 530 nm to 620 nm.

(Claim 2)
The method for producing a photosensitive lithographic printing plate according to claim 1, wherein the photosensitive layer contains at least one compound selected from a titanocene compound, an iron arene complex compound, and a biimidazole compound as a photopolymerization initiator.

(Claim 3)
The method for producing a photosensitive lithographic printing plate according to claim 2, wherein the photosensitive layer further contains a polyhalogen compound as a photopolymerization initiator.

(Claim 4)
The method for producing a photosensitive lithographic printing plate according to claim 3, wherein the polymerizable ethylenically unsaturated bond-containing compound has a tertiary amino group in the molecule.

(Claim 5)
Photosensitivity having a photosensitive layer containing (A) a polymerizable, ethylenically unsaturated bond-containing compound and (B) a photopolymerization initiator on a support and exposed to a laser beam having an emission wavelength of 350 nm to 500 nm. A method for using a lithographic printing plate, comprising at least an exposure step, a development step, and a printing step, wherein any one of the exposure step, the development step, and the printing step has an emission wavelength maximum at 530 nm to 620 nm. A method for using a photosensitive lithographic printing plate, which is performed under a light-emitting diode lamp.

(Claim 6)
6. The method of using a photosensitive lithographic printing plate according to claim 5, wherein the photosensitive layer contains at least one compound selected from a titanocene compound, an iron arene complex compound, and a biimidazole compound as a photopolymerization initiator.

(Claim 7)
The method for using a photosensitive lithographic printing plate according to claim 6, wherein the photosensitive layer further contains a polyhalogen compound as a photopolymerization initiator.

(Claim 8)
The method for using a photosensitive lithographic printing plate according to claim 7, wherein the polymerizable ethylenically unsaturated bond-containing compound has a tertiary amino group in the molecule.

(Claim 9)
A photosensitive lithographic printing plate produced by the method of producing a photosensitive lithographic printing plate according to claim 1 is used by the method of using the photosensitive lithographic printing plate according to claim 5. How to use the plate.

  Production method and use of a photosensitive lithographic printing plate that provides printing with excellent workability, printing durability, stain recovery, printability (wide printing latitude), and excellent dot quality of printed matter. A method can be provided.

  The present invention has a photosensitive layer containing (A) a polymerizable, ethylenically unsaturated bond-containing compound and (B) a photopolymerization initiator on a support, and is exposed by laser light having an emission wavelength of 350 nm to 500 nm. A method for producing a photosensitive lithographic printing plate comprising at least a coating process, a drying process, a cutting process, and an inspection / sorting process, the coating process, the drying process, the cutting process, and the inspection / sorting process. Any one of the steps is performed under a light-emitting diode lamp having an emission wavelength maximum at 530 to 620 nm.

  The present invention also provides a laser beam having an emission wavelength of 350 nm to 500 nm, having a photosensitive layer containing (A) a polymerizable, ethylenically unsaturated bond-containing compound and (B) a photopolymerization initiator on a support. The method of using a photosensitive lithographic printing plate exposed by the method includes at least an exposure step, a development step, and a printing step, and any one of the exposure step, the development step, and the printing step has a maximum emission wavelength. Is performed under a light emitting diode lamp having a wavelength of 530 nm to 620 nm.

  The manufacturing process of the photosensitive lithographic printing plate starts from the preparation process of the support for the printing plate, but the subject of the present invention is accompanied by the improvement of the working environment for handling the photosensitive material. This is related to the step of applying an object.

  Among the manufacturing processes of the photosensitive lithographic printing plate, the processes after the coating process include a coating process, a drying process, a cutting process, and an inspection / sorting process.

  Depending on the printing plate, a matting process, an aging process, a packaging process, and the like may be added thereto.

  In addition, examples of the printing plate use process include an exposure process, a development process, and a printing process.

  In the present invention, the coating process, the drying process, the cutting process, the inspection / sorting process, the packaging process, the exposure process, the developing process, and the printing process are not limited to each process itself, but enter the process as a pre-stage of the process. What is normally recognized as a series of operations in the process, such as the state of being prepared or waiting as much as possible and the state of being temporarily held in the process after the process is completed and before moving to the next process It means that the process and its surrounding work space.

  Taking the drying process as an example, the drying process itself is usually performed in a dryer. The belt-like support on which the photosensitive composition is applied is conveyed between the applicator and the dryer by a roller or the like before entering the dryer.

  Since the inside of the dryer is usually a dark room without light, in this case, the problem that the applied photosensitive layer is exposed to light by a safety light does not occur.

  On the other hand, the dryer itself may be automatically operated. However, if the operator checks or operates the instrument related to the dryer to check or prepare the operation status, work around the drying process When the space is under the light-emitting diode lamp of the present invention, a printing plate having a higher workability than red or the like and having excellent printability as will be described later, particularly in terms of color identification.

  In the method for producing a photosensitive lithographic printing plate of the present invention, at least one of a coating process, a drying process, a cutting process, and an inspection / sorting process is performed under a light emitting diode lamp having an emission wavelength maximum of 530 nm to 620 nm. However, it is most preferable to carry out all of these steps under the light-emitting diode lamp.

  Next, the photosensitive lithographic printing plate used in the production method and use method of the present invention will be described.

  The photosensitive lithographic printing plate according to the present invention has a photosensitive layer containing (A) a polymerizable, ethylenically unsaturated bond-containing compound and (B) a photopolymerization initiator on a support, and an emission wavelength of 350 nm to It is a photosensitive lithographic printing plate exposed by laser light having 500 nm.

((A) Polymerizable, ethylenically unsaturated bond-containing compound)
The polymerizable ethylenically unsaturated bond-containing compound according to the present invention is a polymerizable compound having an ethylenically unsaturated bond in the molecule, and is generally used for general radical polymerizable monomers and ultraviolet curable resins. Polyfunctional monomers having a plurality of addition-polymerizable ethylenic double bonds in the molecule used, and polyfunctional oligomers can be used.

  These polymerizable ethylenic double bond-containing compounds are not particularly limited, but preferred examples include 2-ethylhexyl acrylate, 2-hydroxypropyl acrylate, glycerol acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, nonylphenoxy. Monofunctional acrylic acid esters such as ethyl acrylate, tetrahydrofurfuryloxyethyl acrylate, tetrahydrofurfuryloxyhexanolide acrylate, ε-caprolactone adduct of 1,3-dioxane alcohol, 1,3-dioxolane acrylate, or Methacrylic acid, itaconic acid, crotonic acid, maleic acid, etc. in which these acrylates are replaced with methacrylate, itaconate, crotonate, and maleate. Tel, for example, ethylene glycol diacrylate, triethylene glycol diacrylate, pentaerythritol diacrylate, hydroquinone diacrylate, resorcin diacrylate, hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, hydroxypivalate neo Diacrylate of pentyl glycol, diacrylate of neopentyl glycol adipate, diacrylate of ε-caprolactone adduct of neopentyl glycol hydroxypivalate, 2- (2-hydroxy-1,1-dimethylethyl) -5-hydroxymethyl- 5-ethyl-1,3-dioxane diacrylate, tricyclodecane dimethylol acrylate, tricyclodecane dimethylo Difunctional acrylic acid esters such as ε-caprolactone adduct of diacrylate, diglycidyl ether diacrylate of 1,6-hexanediol, or methacrylic acid, itacon in which these acrylates are replaced with methacrylate, itaconate, crotonate, maleate Acids, crotonic acid, maleic esters such as trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, trimethylolethane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, Dipentaerythritol hexaacrylate, ε-cap of dipentaerythritol hexaacrylate Lactone adducts, pyrogallol triacrylate, propionic acid / dipentaerythritol triacrylate, propionic acid / dipentaerythritol tetraacrylate, hydroxypivalylaldehyde-modified dimethylolpropane triacrylate and other polyfunctional acrylic acid esters, or these acrylates Examples thereof include methacrylic acid, itaconic acid, crotonic acid, and maleic acid ester instead of methacrylate, itaconate, crotonate, and maleate.

  Prepolymers can also be used as described above. A prepolymer may use together 1 type, or 2 or more types, and may mix and use the above-mentioned monomer and / or oligomer.

  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 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, trimethylolpropane benzoic acid benzoic acid. Addition-polymerizable oligomers and prepolymers having monomers such as esters, alkylene glycol type acrylic acid-modified, urethane-modified acrylates, and structural units formed from the monomers can be contained.

  Furthermore, examples of compounds that can be used in combination in the photosensitive layer according to the present invention include phosphate ester compounds containing at least one (meth) acryloyl group. The compound is a compound in which at least a part of the hydroxyl group of phosphoric acid is esterified.

  In addition, JP-A-58-212994, 61-6649, 62-46688, 62-48589, 62-173295, 62-187092, 63- No. 67189, JP-A-1-244891, and the like. Further, "11290 Chemical Products", Chemical Industry Daily, compounds described on pages 286 to 294, "UV / EB curing" The compounds described in "Handbook (raw material)", Kobunshi Shuppankai, pages 11 to 65, and the like 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 the present invention, a polymerizable ethylenically unsaturated bond-containing compound containing a tertiary amino group in the molecule can be preferably used.

  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.

  Further, in the photosensitive layer according to the present invention, a reaction product of 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 also preferably used. In particular, a compound having a tertiary amino group and an amide bond is preferably used.

  Examples of the polyhydric alcohol containing 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) ) -1,2-propanediol and the like, but not limited thereto.

  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- 2,5-diisocyanate, tolylene-2,6-diisocyanate, 1,3-di (isocyanatomethyl) benzene, 1,3-bis (1-isocyanato-1-methylethyl) benzene, and the like. In Not a constant.

  Examples of the compound containing an ethylenic double bond capable of addition polymerization with a hydroxyl group in the molecule include compounds such as MH-1 to MH-13, but are not limited thereto. Preferable examples include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxypropylene-1,3-dimethacrylate, 2-hydroxypropylene-1-methacrylate-3-acrylate, 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 these 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. .
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-isocyanate-1-methylethyl ) Reaction product of benzene (2 mol), 2-hydroxypropylene-1-methacrylate-3-acrylate (2 mol) M-4: Nn-butyldiethanolamine (1 mol), 1,3-di (isocyanate) Natomethyl) benzene (2 mol), 2-hydroxypropylene-1-methacrylate-3-acrylate (2 mol) reaction Product M-5: Reaction product M-6 of N-methyldiethanolamine (1 mol), tolylene-2,4-diisocyanate (2 mol), 2-hydroxypropylene-1,3-dimethacrylate (2 mol): Reaction product M-7 of triethanolamine (1 mol), 1,3-bis (1-isocyanato-1-methylethyl) benzene (3 mol), 2-hydroxyethyl methacrylate (3 mol): ethylenediaminetetraethanol (1 mol), reaction product of 1,3-bis (1-isocyanato-1-methylethyl) benzene (4 mol), 2-hydroxyethyl methacrylate (4 mol). An acrylate or an alkyl acrylate described in JP-A-2-127404 can be used.

  5-80 mass% is preferable with respect to the photosensitive layer, and, as for the addition amount of the polymerizable unsaturated group containing compound, it is more preferable that it is 15-60 mass%.

((B) Photopolymerization initiator)
The photopolymerization initiator according to the present invention is capable of initiating polymerization of an ethylenically unsaturated bond-containing compound that can be polymerized by image exposure, and is preferably used as a titanocene compound, iron arene complex compound, biimidazole. A compound, a monoalkyltriarylborate compound, and a trihaloalkyl compound.

(Titanocene compound)
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.

(Iron arene complex compound)
The iron arene complex compound according to the present invention is a compound represented by the following general formula (a).

Formula (a) [A-Fe-B] ⁺ X ⁻
In the formula, A represents a substituted or unsubstituted cyclopentadienyl group or a cyclohexadienyl group. In the formula, B represents a compound having an aromatic ring. In the formula, X ⁻ represents an anion.

Specific examples of the compound having an aromatic ring include benzene, toluene, xylene, cumene, naphthalene, 1-methylnaphthalene, 2-methylnaphthalene, biphenyl, fluorene, anthracene, and pyrene. Examples of X ⁻ include PF ₆ ⁻ , BF ₄ ⁻ , SbF ₆ ⁻ , AlF ₄ ⁻ , CF ₃ SO ₃ ^{− and the} like. Examples of the substituent of the substituted cyclopentadienyl group or cyclohexadienyl group include alkyl groups such as methyl and ethyl groups, cyano groups, acetyl groups, and halogen atoms.

  It is preferable to contain an iron arene complex compound in the ratio of 0.1-20 mass% with respect to the compound which has a group which can superpose | polymerize, More preferably, it is 0.1-10 mass%.

Specific examples of the iron arene complex compound 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-benzene Sulfonamide) (η5-cyclopentadienyl) iron (2) tetrafluoroborate Fe-18: (η6-benzamide) (η5-cyclopentadienyl) iron (2) hexafluorophosphate Fe-19: (η6-cyano Benzene) (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).

(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 because the above-described effects can be obtained.

  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 photoinitiator 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 layer.

(Trihaloalkyl compound)
The photosensitive layer of the present invention preferably contains a trihaloalkyl compound as a photopolymerization initiator. The trihaloalkyl compound is a compound having a trihaloalkyl group, and particularly preferably used when the polymerizable ethylenically unsaturated bond-containing compound contains a polymerizable ethylenically unsaturated bond-containing compound containing a group that can be oxidized by light. It is done. As a compound containing a trihaloalkyl group, a compound containing chlorine or bromine is particularly suitable.

  As the trihaloalkyl group, a trihalomethyl group is preferable, and it is preferable that the trihaloalkyl group is bonded to an aromatic carbocycle or a heterocycle directly or via a continuously conjugated chain. Preferred are those having a triazine ring having two trihalomethyl groups as a mother nucleus, particularly the compounds described in EP-A-137452, DE-A-2118259 and 2243621. These compounds exhibit strong light absorption in the near ultraviolet region, for example, 350 to 400 nm. Combination initiators that do not absorb themselves or absorb very little light in the spectral region of the copying light, for example trihalomethyltriazines containing substituents with short electronic systems or aliphatic substituents that allow mesomeries; Is also appropriate. Likewise suitable are compounds having different basic skeletons and absorbing light in the short-wave ultraviolet region, such as phenyl trihalomethyl sulfone or phenyl trihalomethyl ketone, such as phenyl tribromomethyl sulfone.

  Preferred trihaloalkyl compounds include BR1 to BR76, more preferably BR2 to BR47. In addition, the compound which substituted the halogen atom from bromine to chlorine can also be used suitably for these compounds in this invention.

  The content of the photopolymerization initiator used in the present invention is preferably 0.1% by mass to 20% by mass and particularly preferably 0.5% by mass to 15% by mass with respect to the polymerizable ethylenically unsaturated bond-containing compound. I like it.

  Examples of the monoalkyl triaryl borate compound include compounds described in JP-A-62-150242 and JP-A-62-143044, and more preferable specific examples include tetra-n-butylammonium n-butyl-tri. Naphthalen-1-yl-borate, tetra-n-butylammonium n-butyl-triphenyl-borate, tetra-n-butylammonium n-butyl-tri- (4-tert-butylphenyl) -borate, tetra-n-butylammonium Examples include n-hexyl root- (3-chloro-4-methylphenyl) -borate, tetra-n-butylammonium n-hexyl root- (3-fluorophenyl) -borate and the like.

  In addition, any photopolymerization initiator can be used in combination. For example, J. et al. Carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo, diazo compounds, halogen compounds, and photoreductive dyes as described in Chapter 5 of “Light Sensitive Systems” by J. Kosar Etc. More specific compounds are disclosed in British Patent 1,459,563.

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

  Benzoin derivatives such as benzoin methyl ether, benzoin-i-propyl ether, α, α-dimethoxy-α-phenylacetophenone; benzophenone, 2,4-dichlorobenzophenone, methyl o-benzoylbenzoate, 4,4′-bis (dimethyl) Benzophenone derivatives such as amino) benzophenone; thioxanthone derivatives such as 2-chlorothioxanthone and 2-i-propylthioxanthone; anthraquinone derivatives such as 2-chloroanthraquinone and 2-methylanthraquinone; N-methylacridone, N-butylacridone and the like In addition to α, α-diethoxyacetophenone, benzyl, fluorenone, xanthone and uranyl compounds, JP-B-59-1281, 61-9621 and JP-A-60-60104 Triazine derivatives; organic peroxides described in JP-A-59-1504 and JP-A-61-243807; JP-B-43-23684, JP-A-44-6413, JP-A-44-6413, JP-A-47-1604, and US patents Diazonium compounds described in US Pat. No. 3,567,453; organic azide compounds described in US Pat. Nos. 2,848,328 and 2,852,379 and 2,940,853; O-quinonediazides described in JP-A Nos. 13109, 38-18015 and 45-9610; JP-B-55-39162, JP-A-59-14023 and “Macromolecules”, Vol. 10, 1307 Various onium compounds described on page 1977; azo compounds described in JP-A-59-142205 Compound: described in JP-A-1-54440, European Patents 109,851, 126,712 and “Journal of Imaging Science (J. Imag. Sci.)”, Vol. 30, 174 (1986) (Oxo) sulfonium organoboron complexes described in Japanese Patent Application Nos. 4-56831 and 4-89535; “Coordination Chemistry Review” Vol. 84, (pp. 85-277) 1988) and transition metal complexes containing a transition metal such as ruthenium described in JP-A-2-182701; 2,4,5-triarylimidazole dimer described in JP-A-3-209477; carbon tetrabromide, Organic halogen compounds described in JP-A-59-107344 Things, etc.

(Polymer binder)
The photosensitive layer according to the present invention preferably contains a polymer binder for supporting a polymerization initiator and a polymerizable, ethylenically unsaturated bond-containing compound.

  Examples of the polymer binder include acrylic polymer, polyvinyl butyral resin, polyurethane resin, polyamide resin, polyester resin, epoxy resin, phenol resin, polycarbonate resin, polyvinyl butyral resin, polyvinyl formal resin, shellac, and other natural resins. Can be used. Two or more of these may be used in combination.

  A vinyl copolymer obtained by copolymerization of acrylic monomers is preferred. Furthermore, the copolymer composition of the polymer binder is preferably a copolymer of (a) a carboxyl group-containing monomer, (b) a methacrylic acid alkyl ester, or an 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 alkyl methacrylates and alkyl esters include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, nonyl methacrylate. , Decyl methacrylate, undecyl methacrylate, dodecyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, nonyl acrylate, acrylic In addition to unsubstituted alkyl esters such as decyl acid, undecyl acrylate and dodecyl acrylate, cyclic alkyl esters such as cyclohexyl methacrylate and cyclohexyl acrylate Substituted alkyl esters such as benzyl methacrylate, 2-chloroethyl methacrylate, N, N-dimethylaminoethyl methacrylate, glycidyl methacrylate, benzyl acrylate, 2-chloroethyl acrylate, N, N-dimethylaminoethyl acrylate, and glycidyl acrylate Also mentioned.

  Furthermore, the polymer binder according to the present invention can use monomers described in the following (1) to (14) 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.

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

  The vinyl polymer can be produced by ordinary solution polymerization. It can also be produced by bulk polymerization or suspension polymerization. The polymerization initiator is not particularly limited, and examples thereof include azobis-based radical generators such as 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobis (2-methylbutyro). Nitrile) and the like. Moreover, the usage-amount of these polymerization initiators is 0.05-10.0 mass parts normally with respect to 100 mass parts of whole monomers used for forming a copolymer (preferably 0.1-5 mass). Part). Examples of the solvent used for the solution polymerization include ketone-based, ester-based, and aromatic-based organic solvents, among which toluene, ethyl acetate, benzene, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, and the like. In general, a good solvent for an acrylic polymer is used, and a solvent having a boiling point of 60 to 120 ° C. is particularly preferable. In the case of solution polymerization, the above solvent is used, and the reaction temperature is usually 40 to 120 ° C. (preferably 60 to 110 ° C.) and the reaction time is usually 3 to 10 hours (preferably 5 to 8 hours). it can. After completion of the reaction, the solvent is removed to obtain a copolymer. Further, the double bond introduction reaction described later can be carried out without removing the solvent.

  The molecular weight of the resulting copolymer can be adjusted by adjusting the solvent used and the reaction temperature. The solvent, reaction temperature, and the like used to obtain the desired molecular weight copolymer can be appropriately determined depending on the monomer used. Moreover, the molecular weight of the copolymer obtained can also be adjusted by mixing a specific solvent with the said solvent. Examples of such solvents include mercaptans (eg, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, mercaptoethanol, etc.), carbon tetrachloride (eg, carbon tetrachloride, butyl chloride, propylene chloride). Etc.). The ratio of mixing these solvents with the solvent used in the above reaction can be appropriately determined depending on the monomer, solvent, reaction conditions, etc. used in the reaction.

  Furthermore, the polymer binder according to the present invention is preferably a vinyl polymer having a carboxyl group and a polymerizable double bond in the side chain. For example, an unsaturated bond-containing vinyl copolymer obtained by addition-reacting 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 preferred as a polymer binder.

  Specific examples of the compound containing both an unsaturated bond and an epoxy group in the molecule include glycidyl acrylate, glycidyl methacrylate, and an epoxy group-containing unsaturated compound described in JP-A No. 11-271969. In addition, an unsaturated bond-containing vinyl copolymer obtained by adding a compound having a (meth) acryloyl group and an isocyanate group in the molecule to a hydroxyl group present in the molecule of the vinyl polymer is also high. Preferred as a molecular binder. Compounds having both an unsaturated bond and an isocyanate group in the molecule include vinyl isocyanate, (meth) acrylic isocyanate, 2- (meth) acryloyloxyethyl isocyanate, m- or p-isopropenyl-α, α'-dimethylbenzyl. Isocyanates are preferred, and (meth) acrylic isocyanate, 2- (meth) acryloyloxyethyl isocyanate and the like can be mentioned.

  A known method can be used for the 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. For example, the reaction temperature is 20 to 100 ° C., preferably 40 to 80 ° C., particularly preferably at the boiling point (under reflux) of the solvent used, and the reaction time is 2 to 10 hours, preferably 3 to 6 hours. Can do. Examples of the solvent to be used include those used in the polymerization reaction of the vinyl copolymer. In addition, after the polymerization reaction, the solvent can be used as it is for the introduction reaction of the alicyclic epoxy group-containing unsaturated compound without removing the solvent. The reaction can be performed in the presence of a catalyst and a polymerization inhibitor as necessary.

  Here, the catalyst is preferably an amine-based or ammonium chloride-based material, and specifically, the amine-based material is triethylamine, tributylamine, dimethylaminoethanol, diethylaminoethanol, methylamine, ethylamine, n-propylamine. , Isopropylamine, 3-methoxypropylamine, butylamine, allylamine, hexylamine, 2-ethylhexylamine, benzylamine, and the like, and ammonium chloride-based substances include triethylbenzylammonium chloride and the like.

  When using these as a catalyst, what is necessary is just to add in 0.01-20.0 mass% with respect to the alicyclic epoxy group containing unsaturated compound to be used. In addition, as polymerization inhibitors, hydroquinone, hydroquinone monomethyl ether, tert-butyl hydroquinone, 2,5-di-tert-butyl hydroquinone, methyl hydroquinone, p-benzoquinone, methyl-p-benzoquinone, tert-butyl-p-benzoquinone 2,5-diphenyl-p-benzoquinone and the like, and the amount used is 0.01 to 5.0% by mass with respect to the alicyclic epoxy group-containing unsaturated compound to be used. The progress of the reaction may be determined by measuring the acid value of the reaction system and stopping the reaction when the acid value becomes zero.

  A known method can be used for the addition reaction of a compound having a (meth) acryloyl group and an isocyanate group in the molecule to a hydroxyl group present in the molecule of the vinyl polymer. For example, the reaction temperature is usually 20 to 100 ° C., preferably 40 to 80 ° C., particularly preferably at the boiling point (under reflux) of the solvent used, and the reaction time is usually 2 to 10 hours, preferably 3 to 6 hours. It can be carried out. Examples of the solvent to be used include solvents used in the polymerization reaction of the polymer copolymer. Further, after the polymerization reaction, the solvent can be used as it is for the introduction reaction of the isocyanate group-containing unsaturated compound without removing the solvent. The reaction can be performed in the presence of a catalyst and a polymerization inhibitor as necessary. Here, the catalyst is preferably a tin-based or amine-based substance, and specific examples include dibutyltin laurate and triethylamine.

  The catalyst is preferably added in the range of 0.01 to 20.0 mass% with respect to the compound having a double bond to be used. In addition, as polymerization inhibitors, hydroquinone, hydroquinone monomethyl ether, tert-butyl hydroquinone, 2,5-di-tert-butyl hydroquinone, methyl hydroquinone, p-benzoquinone, methyl-p-benzoquinone, tert-butyl-p-benzoquinone 2,5-diphenyl-p-benzoquinone and the like, and the amount used is usually 0.01 to 5.0% by mass with respect to the isocyanate group-containing unsaturated compound to be used. The progress of the reaction may be determined by determining the presence or absence of an isocyanato group in the reaction system using an infrared absorption spectrum (IR), and stopping the reaction when the absorption disappears.

  The vinyl polymer having a carboxyl group and a polymerizable double bond in the side chain that can be used in the present invention is preferably 50 to 100% by mass, and 100% by mass in the total polymer binder. It is more preferable.

  The content of the polymer binder in the photopolymerizable photosensitive layer is preferably in the range of 10 to 90% by mass, more preferably in the range of 15 to 70% by mass, and the content in the range of 20 to 50% by mass. This is particularly preferable from the viewpoint of sensitivity.

(Dye having an absorption maximum wavelength of 350 to 500 nm)
The photosensitive layer of the present invention is image-exposed with a laser beam having an emission wavelength of 350 to 500 nm. The photosensitive layer preferably contains a sensitizing dye having an absorption maximum in the wavelength range of 350 to 500 nm.

  Examples of these dyes include cyanine, merocyanine, porphyrin, spiro compound, ferrocene, fluorene, fulgide, imidazole, perylene, phenazine, phenothiazine, acridine, azo compound, diphenylmethane, triphenylmethane, triphenylamine, coumarin derivative, quinacridone, Examples include indigo, styryl, pyrylium compounds, pyromethene compounds, pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, thiobarbituric acid derivatives, ketoalcohol borate complexes, and the like.

  Among these sensitizing dyes, for example, coumarin derivatives of B-1 to B-22 in JP-A-8-129258, coumarin derivatives of D-1 to D-32 in JP-A-2003-21901, and JP-A-2002. No. 1-363206, 1 to 21 coumarin derivatives, JP 2002-363207 A to 40 coumarin derivatives, JP 2002-363208 A to 34 coumarin derivatives, JP 2002-363209 A, 1 to 56 coumarin derivatives and the like can be preferably used.

(Various additives)
In addition to the components described above, the photopolymerizable photosensitive layer of the present invention contains unnecessary polymerization of an ethylenically unsaturated double bond monomer that can be polymerized during the production or storage of a photosensitive lithographic printing plate material. In order to inhibit, hindered phenolic compounds, hindered amine compounds and other polymerization inhibitors may be added.

  Examples of hindered phenol compounds include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,2′-methylenebis (4-methyl-6-t-butylphenol), 4,4 '-Butylidenebis (3-methyl-6-tert-butylphenol), tetrakis- [methylene-3- (3', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate] methane, bis [3,3 '-Bis- (4'-hydroxy-3'-t-butylphenyl) butyric acid] glycol ester, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl)- 4-methylphenyl acrylate, 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphene Acrylate, etc., preferably 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate having a (meth) acrylate group, 2- [ And 1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate.

  Examples of hindered amine compounds include bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1- [ 2- [3- (3,5-di-tert-butyl-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy]- 2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1, 3,8-triazaspiro [4.5] decane-2,4-dione and the like.

  Other polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol) Hindered amines such as 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxylamine cerium salt, 2,2,6,6, -tetramethylpiperidine derivatives, etc. It is done.

  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. Also, if necessary, higher fatty acid derivatives such as behenic acid and behenic acid amide are added to prevent polymerization inhibition by oxygen, or unevenly distributed on the surface of the photopolymerizable photosensitive layer during the drying process after coating. You may let them. The amount of the higher fatty acid derivative added is preferably about 0.5% to about 10% of the total composition.

  In the photosensitive layer according to the present invention, in addition to the above-described components, a colorant can be used. As the colorant, conventionally known ones including commercially available ones can be suitably used. 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 sensitizing dye 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%.

  Further, a plasticizer can be contained in order to improve the adhesion to the support. Plasticizers include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, didodecyl phthalate, diisodecyl phthalate, butyl benzyl phthalate, diisononyl phthalate, ethyl phthalyl ethyl Examples include glycol, dimethyl isophthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin. The amount of the plasticizer added is preferably about 0 to 3% by mass, more preferably 0.1 to 2% by mass, based on the total solid content of the coating composition.

  In addition, a coating property improving agent such as a surfactant necessary for coating the photosensitive layer can be contained within a range not impairing the performance of the present 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 of the photosensitive layer.

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

  Examples of the support of the present invention include a metal plate such as aluminum, stainless steel, chromium and nickel, and a laminate obtained by laminating or vapor-depositing the above metal thin film on a plastic film such as a polyester film, a polyethylene film and a polypropylene film.

  Moreover, although what hydrophilized the surface, such as a polyester film, a vinyl chloride film, a nylon film, etc. can be used, an aluminum support body is used preferably. In the case of an aluminum support, pure aluminum or an aluminum alloy is 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. . Further, the aluminum support having a roughened surface is used for water retention.

  Prior to roughening (graining treatment), it is preferable to perform 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. Examples of the roughening method include a mechanical method and a method of etching by electrolysis.

  The mechanical roughening method used is not particularly limited, but a brush polishing method and a honing polishing method are preferable.

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

After the surface is roughened by the electrochemical surface roughening method, it is preferably immersed in an acid or alkali 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.

  The mechanical surface roughening method and the electrochemical surface roughening method may each be used alone for roughing, or the mechanical surface roughening method followed by the electrochemical surface roughening method. You may roughen.

  Following the 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.

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

  Furthermore, after performing these treatments, water-soluble resins such as polyvinylphosphonic acid, polymers and copolymers having a sulfonic acid group in the side chain, polyacrylic acid, water-soluble metal salts (for example, zinc borate) or Also suitable are those coated with a yellow dye, amine salt or the like. Further, a sol-gel treated substrate in which a functional group capable of causing an addition reaction by a radical as disclosed in JP-A No. 5-304358 is covalently used.

(Protective layer)
A protective layer is preferably provided on the upper side of the photosensitive layer according to the present invention. The protective layer (oxygen barrier layer) preferably has high solubility in a developing solution (generally an alkaline aqueous solution) described later.

  The material constituting the protective layer is preferably polyvinyl alcohol, polysaccharide, polyvinyl pyrrolidone, polyethylene glycol, gelatin, glue, casein, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, hydroxyethyl starch, gum arabic, sucrose octaacetate, ammonium alginate , Sodium alginate, polyvinylamine, polyethylene oxide, polystyrene sulfonic acid, polyacrylic acid, water-soluble polyamide, polyvinylpyrrolidone copolymer, and the like. These compounds can be used alone or in combination of two or more as a protective layer coating composition. A particularly preferred compound is polyvinyl alcohol.

  In order to prepare the protective layer coating composition, the above-mentioned material can be dissolved in a suitable solvent to form a coating solution, which is coated on the photopolymerizable photosensitive layer according to the present invention and dried. Thus, a protective layer can be formed. The thickness of the protective layer is preferably from 0.1 to 5.0 μm, particularly preferably from 0.5 to 3.0 μm. The protective layer can further contain a surfactant, a matting agent and the like as required.

  As the method for coating the protective layer, known coating methods mentioned for the coating of the photosensitive layer can be suitably used. The drying temperature of the protective layer is preferably lower than the drying temperature of the photosensitive layer, preferably the difference from the photosensitive layer drying temperature is 10 ° C. or more, more preferably 20 ° C. or more, and the upper limit is about 50 ° C. at most. .

  Moreover, it is preferable that the drying temperature of a protective layer is lower than the glass transition temperature (Tg) of the binder which a photosensitive layer contains. The difference between the drying temperature of the protective layer and the glass transition temperature (Tg) of the binder contained in the photosensitive layer is preferably 20 ° C. or higher, more preferably 40 ° C. or higher, and the upper limit is about 60 ° C. at most.

  In the coating process of the photosensitive lithographic printing plate used in the present invention, the above-described components of the photosensitive layer and various additives are dissolved in an appropriate solvent and coated on a support.

  The type of the solvent is not particularly limited as long as it has sufficient solubility for each of the above-described components and gives good coating properties.

  Examples of such solvents include cellosolv solvents such as methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, Propylene glycol solvents such as propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether, butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, diethyl oxalate, ethyl pyruvate, ethyl-2-hydroxybutyrate Rate, ethyl acetoacetate, methyl lactate, ethyl lactate, 3-methoxy Ester solvents such as methyl lopionate, alcohol solvents such as heptanol, hexanol, diacetone alcohol, furfuryl alcohol, ketone solvents such as cyclohexanone, methyl amyl ketone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. In addition to the polar solvent, acetic acid, a mixed solvent thereof, a mixed solvent obtained by adding an aromatic hydrocarbon thereto, and the like can be given.

  The use ratio of the solvent is usually in the range of 1 to 20 (mass ratio) times the total amount of the photosensitive composition.

  In the coating step, a conventionally known method such as spin coating, wire bar coating, dip coating, air knife coating, roll coating, blade coating, curtain coating or the like is performed.

  The coating amount is usually in the range of 0.3 to 7 μm, preferably 0.5 to 5 μm, and more preferably 1 to 3 μm as a dry film thickness.

  Next, in the drying step after coating, drying is usually performed in the range of 30 to 170 ° C., preferably 40 to 150 ° C., and the residual solvent is usually 10% by mass or less in the photosensitive layer.

  After the drying step, an aging step is performed as necessary. The aging process is to hold the printing plate under heating under certain conditions, but the development latitude can be widened through the aging process.

  There is a cutting step of cutting the printing plate into a predetermined size before or after the aging step.

  In the cutting process, a printing plate having a predetermined size is cut according to various uses.

  However, even after this cutting step, after passing through another step, there may be a step of finally removing a part of the printing plate for the purpose of dimension alignment and edge processing.

  Next, in the inspection / sorting step, it is determined whether or not the photosensitive lithographic printing plate as the final product is valuable as a product.

  Printing plates that are judged to have no commercial value in the inspection / sorting process are recycled or discarded and are not shipped. The inspection / sorting step is performed by visual inspection by an operator, computer processing of information obtained from a camera, or a combination thereof. In the inspection / sorting process, the surface of the photosensitive layer is inspected for scratches or uneven coating.

  This final inspection / selection process is necessary for final selection as a product. However, in some cases, a process for inspecting and selecting surface defects between the processes before the cutting process is provided.

  The printing plate to be shipped as a product by the inspection / sorting process is arranged in a form for shipping. Depending on the type of printing plate, a plurality of printing plates are mounted on a horizontal or vertical mounting table. In this case, it is supplied to the user in a mounted state, and is set as a printing plate supply mounting table for the exposure apparatus.

  In addition, when the printing plate is placed on the printing plate supply platform of the exposure apparatus on the user side, the supplier packs it using an outer packaging box such as a cardboard box for transportation to the user. (Packaging process) The printing plate mounted on the mounting table or packaged is shipped and finally supplied to the user.

  Next, as a process of making a plate using a photosensitive lithographic printing plate and printing, there are an exposure process, a development process, and a printing process.

(Plate making method)
In the method of use of the present invention, the photosensitive lithographic printing plate is exposed with a laser in the ultraviolet region of 350 nm to 500 nm. The following can be used as an available laser light source having a wavelength of 350 to 500 nm. As gas laser, Ar ion laser (364 nm, 351 nm), Kr ion laser (356 nm, 351 nm), He—Cd laser (441 nm), and solid laser as Nd: YAG (YVO4) and SHG crystal × 2 combinations ( 355 nm), a combination of Cr: LiSAF and SHG crystal (430 nm), as a semiconductor laser system, a combination of KNbO 3, ring resonator (430 nm), waveguide type wavelength conversion element and AlGaAs, InGaAs semiconductor (380 nm to 450 nm), A combination of a waveguide type wavelength conversion element and AlGaInP and an AlGaAs semiconductor (300 nm to 350 nm), AlGaInN (350 nm to 450 nm), N2 laser (337 nm, pulse 0.1 to 10 mJ), XeF (3 1 nm, pulse 10 to 250 mJ), and the like. Among these, an AlGaInN semiconductor laser (commercially available InGaN-based semiconductor laser 400 to 410 nm) is preferable in terms of wavelength characteristics and cost.

  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.

(Automatic processor)
In the method of use of the present invention, a method of developing a photosensitive lithographic printing plate material using an automatic developing machine is a preferable embodiment because the effects of the present invention are effective.

  The automatic developing machine is preferably provided with a mechanism for automatically replenishing a required amount of replenisher to the developing bath, and preferably provided with a mechanism for discharging a developer exceeding a certain amount, preferably the developing bath. Is provided with a mechanism for automatically replenishing the required amount of water, preferably a mechanism for detecting the plate passing, preferably a mechanism for estimating the processing area of the plate based on the detection of the plate passing And preferably a mechanism for controlling the replenishment amount and / or replenishment timing of replenisher and / or water to be replenished based on the detection of the plate and / or the estimation of the processing area. Preferably, a mechanism for controlling the temperature of the developer is provided, preferably a mechanism for detecting the pH and / or conductivity of the developer is provided, preferably the pH and / or conductivity of the developer. Mechanism for controlling the replenishment amount and / or replenishment timing of replenishment solution and / or water tries to refill the original has been granted.

  The automatic processor may have a pretreatment unit that immerses the plate in the pretreatment liquid before the development step. The pretreatment unit is preferably provided with a mechanism for spraying the pretreatment liquid onto the plate surface, and preferably provided with a mechanism for controlling the temperature of the pretreatment liquid to an arbitrary temperature of 25 ° C to 55 ° C. A mechanism for rubbing the plate surface with a roller-like brush is preferably provided. Moreover, water etc. are used as this pretreatment liquid.

(Post-processing)
The developed plate is subjected to post-treatment with rinse water containing a washing water, a surfactant or the like, a finisher mainly composed of gum arabic or a starch derivative, or a protective gum solution, and then subjected to printing.

  These post-processing are generally performed using an automatic developing machine including a developing unit and a post-processing unit.

  As the post-treatment liquid, a method of spraying from a spray nozzle or a method of immersing and conveying in a treatment tank filled with the treatment liquid is used. There is also known a method in which a small amount of washing water after development is supplied to the plate surface and washed, and the waste solution is reused as dilution water for the developer stock solution. In such automatic processing, processing can be performed while each replenisher is replenished with each replenisher according to the processing amount, operating time, and the like. In addition, a so-called disposable processing method in which treatment is performed with a substantially unused post-treatment liquid can also be applied. The lithographic printing plate obtained by such processing is loaded on an offset printing machine and used for printing a large number of sheets.

  In the plate making method of the present invention, in the case of a photosensitive lithographic printing plate material having an overcoat layer, a plate making method including a step of washing with pre-development washing water is a preferred embodiment.

(printing)
The photosensitive lithographic printing plate material is subjected to plate making, post-processing, and printing.

  Printing can be performed using a general lithographic printing machine.

  Before the exposure process, the supplied printing plate is placed on the printing plate supply platform of the exposure apparatus. If the printing plate is packaged, the packaging box is opened and printed. Remove the plate and place it.

  From the exposure device to the development device and the printing device, the printing plate is transported by an automatic transport machine, which may be consistently automated until a printed product is produced. The printing plate may be transferred to the process. Even if the operator handles the printing plate directly, even if the transport is automated, the operator checks the instruments related to the exposure device, developing device, and printing device in order to check or prepare the operating status. Alternatively, if the working space around each process is a light emitting diode lamp according to the present invention, the workability is higher than that of red or the like.

  The light emission wavelength maximum of the light emitting diode used in the above-described production method and use method of the present invention is 530 nm to 620 nm, particularly preferably 550 nm to 600 nm.

  The higher the illuminance, the better, usually 10 lux to 5000 lux, more preferably 30 lux to 1000 lux.

  A commercially available light-emitting diode lamp can be used, and it is preferable that a plurality of light-emitting diode lamps are arranged in a line or in a planar shape and irradiated. Specific products include TLYH (manufactured by Toshiba), LSLI-560YT (manufactured by ROHM), and the like.

  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 weight 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 A1050 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. This solution 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 . Further, after washing with water for spraying, it was immersed in a 0.4% by mass polyvinylphosphonic acid solution (used by diluting PVPA30 manufactured by Clariant) for 30 seconds to be hydrophilized. The temperature was 85 ° C. 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 support, a photopolymerizable photosensitive layer coating solution 1 having the following composition was applied with a wire bar so as to have a dry weight of 1.5 g / m ² , and dried at 95 ° C. for 1.5 minutes. A sample was obtained.

Further, on the photopolymerization photosensitive layer coating sample, an oxygen barrier layer coating solution having the following composition was coated with a wire bar so as to be 1.8 g / m ² at the time of drying, and dried at 75 ° C. for 1.5 minutes. A photosensitive lithographic printing plate sample having an oxygen barrier layer on the layer was prepared.

  The safe light was manufactured using an EncapSulite R-10 filter in a fluorescent lamp manufactured by FLR40S- / MX National, under an illuminance of 30 lux. This safe light is dark red, and manufacturing work is possible under this safe light, but the manufacturing work efficiency is lower than that under white light.

(Photopolymerizable photosensitive layer coating solution 1)
Ethylenic double bond-containing monomer (NK Oligo U-4HA: Shin-Nakamura Chemical Co., Ltd.)
27.0 parts Ethylenic double bond-containing monomer (NK ester 4G: Shin-Nakamura Chemical Co., Ltd.)
14.0 parts Spectral sensitizing dye (dye-1) 3.0 parts Polymerization initiator listed in Table 1 4.0 parts Acrylic copolymer 1 45.0 parts Phthalocyanine pigment (MHI454: manufactured by Mikuni Dye Co., Ltd.) 0 parts 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (Sumilyzer GS: manufactured by Sumitomo 3M) 0.5 parts Fluorine-based surfactant (FC-4430; manufactured by Sumitomo 3M Limited) 0.5 parts Methyl ethyl ketone 80 parts Cyclohexanone 820 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) 5 parts Cationic modified polyvinyl alcohol (Kuraray C polymer: manufactured by Kuraray) 5 parts Surfactant (Surfinol 465: manufactured by Nissin Chemical Industry Co., Ltd.) 0.5 part Water 900 Part <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 added to pH = 12.9 (the balance is water)
<< Evaluation of photosensitive lithographic printing plate >>
(Evaluation of printing durability)
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 is 50 μJ / cm ² , exposure is performed at 2400 dpi (dpi represents the number of dots per 2.54 cm). Went. After exposure, a preheating portion for heat-treating the photosensitive lithographic printing plate at 105 ° C. for 10 seconds, a pre-water washing portion for removing the oxygen blocking layer before development, a development portion filled with a developer having the following composition, and a developer attached to the plate surface Developed with a CTP automatic developing machine (PHW23-V: manufactured by Technigraph) equipped with a washing section for removing water, and a gum solution for protecting the image area (GW-3: manufactured by Mitsubishi Chemical Corporation) Processing was carried out to obtain a lithographic printing plate.

  The produced 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 printing 500 sheets continuously, 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.

  The printing durability once refers to the operation of wiping with a cleaner after continuous printing of 500 sheets. The more it is, the better. The cleaner uses an Ultra Plate Cleaner (Distributor: Dainichi Seika).

  In the process from exposure to development and printing, it was carried out under safe light under the conditions shown in Table-1.

  The process of being exposed to a safelight includes when a plate is loaded on a plate setter and when printing plate making evaluation is performed after processing.

  The illuminance was a digital illuminometer T-1M (Konica Minolta Sensing).

  The light-emitting diodes were prepared in an array of 5 rows X20 = 100, and the height from the printing plate was adjusted so that the illuminance shown in Table 1 was obtained, and the illuminance shown in Table 1 was obtained. When the light emitting diode was used, the plate-making work efficiency was almost the same at each wavelength, which was higher than that of the dark red safe light.

(Evaluation of stain recovery)
Wipe with a cleaner after continuous printing of 500 sheets, printing was resumed 15 minutes later, and the number of non-image areas was free of background stains. Less is better.

(Evaluation of water width (allowable printing width))
Adjust the dampening water of the printing press (Mitsubishi Heavy Industries, Ltd. DAIYA1F-1), increase the dampening amount, and reduce the dampening water amount from the dial value W1 where the water mark is seen in the solid part. A value obtained by subtracting the dial value W2 in which the ink is entangled in the non-image portion is obtained. The larger the value, the better the tolerance.
(Dot quality rank)
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 is 50 μJ / cm ² , exposure is performed at 2400 dpi (dpi represents the number of dots per 2.54 cm). Went.

  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 having the following composition, and a developer adhered to the plate surface Developed with a CTP automatic developing machine (PHW23-V: manufactured by Technigraph) equipped with a washing unit for removing water and a gum solution for protecting the image area (GW-3: manufactured by Mitsubishi Chemical Corporation) Processing was carried out to obtain a lithographic printing plate.

50% halftone dots were observed with a 100 times magnifier, and the following rank evaluation was performed. Rank 1: The fringe was very large compared to the size of the halftone dots, and the sizes of the halftone dots were completely irregular. The fringe is very large compared to the size of the halftone dot, and the size of the halftone dot is not practical because it is not practical. Level 3: The fringe is large compared to the size of the halftone dot, and the size of the halftone dot is not uniform. Level 5: Unusable for practical use Level 5: Fringe is conspicuous, practical lower limit Level 6: Fringe is well understood, but there is no problem Quality 7: Edges of halftone dots are very sharp, and it is easy to see that there is fringe There is no problem at all. Quality 8: Edges of halftone dots are very sharp and fringes are very small, but high quality 9: Edges of halftone dots are very sharp and no fringes Level 10: Edges of halftone dots In the very sharp, level fringe no (emission spectrum of the light emitting diodes)
Measured using a spectral irradiance meter USR-40D manufactured by USHIO INC.

  From Table 1, it can be seen that according to the method of use of the present invention, a printed matter having excellent printing durability, stain recovery property, printing acceptability and good dot quality can be obtained.

(Example 2)
The same procedure as in Example 1 was performed except that the polymerization initiator was changed to that shown in Table 2. The results are shown in Table 2.

  From Table 2, it can be seen that according to the method of use of the present invention, a printed matter having excellent printing durability, stain recovery property, printing acceptability and good dot quality can be obtained.

(Example 3)
The same procedure as in Example 1 was performed except that the polymerization initiator was changed to those shown in Table 3. The results are shown in Table 3.

  From Table 3, it can be seen that according to the method of use of the present invention, a printed matter having excellent printing durability, stain recovery property, printing tolerance and good dot quality can be obtained.

Example 4
(Preparation of photosensitive lithographic printing plate)
On the support, a photopolymerizable photosensitive layer coating solution 2 having the following composition is applied with a wire bar so that the dried composition becomes 1.5 g / m ² , and dried at 95 ° C. for 1.5 minutes. A sample was obtained. Further, on the photopolymerization photosensitive layer coating sample, an oxygen barrier layer coating solution having the following composition was coated with a wire bar so as to be 1.8 g / m ² at the time of drying, and dried at 75 ° C. for 1.5 minutes. A photosensitive lithographic printing plate sample having an oxygen barrier layer on the layer was prepared.

(Photopolymerizable photosensitive layer coating solution 2)
Ethylene double bond-containing monomer (shown in Table 4) 27.0 parts Ethylene double bond-containing monomer 2 (NK ester 4G: Shin-Nakamura Chemical Co., Ltd.)
14.0 parts Spectral sensitizing dye (dye-1) 3.0 parts Polyhalogen compound (shown in Table 4) 10.0 parts Polymerization initiator (shown in Table 4) 4.0 parts Acrylic copolymer 1 35 0.0 part phthalocyanine pigment (MHI454: manufactured by Gokoku Color Co., Ltd.) 6.0 part 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (Sumilyzer GS) 0.5 parts Fluorine-based surfactant (FC-4430; manufactured by Sumitomo 3M) 0.5 parts Methyl ethyl ketone 80 parts Cyclohexanone 820 parts (Oxygen blocking layer coating solution)
Polyvinyl alcohol (GL-05: manufactured by Nippon Synthetic Chemical Co., Ltd.) 79 parts Polyvinylpyrrolidone (PVP K-30: manufactured by IPS Japan) 10 parts Polyethyleneimine (Lupazole WF: manufactured by BASF) 5 parts Cationic modified polyvinyl alcohol (Kuraray) C polymer: manufactured by Kuraray Co., Ltd.) 5 parts Surfactant (Surfinol 465: manufactured by Nissin Chemical Industry Co., Ltd.) 0.5 part Water 900 parts The same developer as that used in Example 1 was used.

  The results are shown in Table 4.

  From Table 4, it can be seen that according to the method of use of the present invention, a printed matter having excellent printing durability, stain recovery property, printing tolerance and good dot quality can be obtained.

(Example 5)
The same procedure as in Example 4 was performed except that the polymerization initiator was changed to that shown in Table 5.

  From Table 5, it can be seen that according to the method of use of the present invention, a printed matter having excellent printing durability, stain recovery property, printing tolerance and good dot quality can be obtained.

(Example 6)
The same procedure as in Example 4 was performed except that the polymerization initiator was changed to those shown in Table 6.

  From Table 6, it can be seen that according to the method of use of the present invention, a printed matter having excellent printing durability, stain recovery property, printing tolerance and good dot quality can be obtained.

(Example 7)
The same procedure as in Example 1 was conducted except that the photosensitive lithographic printing plate was produced under the conditions shown in Table 7 in the process of producing the photosensitive lithographic printing plate. The production work efficiency using fluorescent lamps or light emitting diodes was almost the same.

  From Table 7, it can be seen that in the production method of the present invention, a printed matter with good dot quality can be obtained.

Claims (9)

Photosensitivity having a photosensitive layer containing (A) a polymerizable, ethylenically unsaturated bond-containing compound and (B) a photopolymerization initiator on a support and exposed to a laser beam having an emission wavelength of 350 nm to 500 nm. A method for producing a lithographic printing plate, comprising at least a coating step, a drying step, a cutting step, and an inspection / sorting step, and any step of the coating step, the drying step, the cutting step, and the inspection / sorting step Is carried out under a light emitting diode lamp having an emission wavelength maximum at 530 nm to 620 nm. The method for producing a photosensitive lithographic printing plate according to claim 1, wherein the photosensitive layer contains at least one compound selected from a titanocene compound, an iron arene complex compound, and a biimidazole compound as a photopolymerization initiator. The method for producing a photosensitive lithographic printing plate according to claim 2, wherein the photosensitive layer further contains a polyhalogen compound as a photopolymerization initiator. The method for producing a photosensitive lithographic printing plate according to claim 3, wherein the polymerizable ethylenically unsaturated bond-containing compound has a tertiary amino group in the molecule. Photosensitivity having a photosensitive layer containing (A) a polymerizable, ethylenically unsaturated bond-containing compound and (B) a photopolymerization initiator on a support and exposed to a laser beam having an emission wavelength of 350 nm to 500 nm. A method for using a lithographic printing plate, comprising at least an exposure step, a development step, and a printing step, wherein any one of the exposure step, the development step, and the printing step has an emission wavelength maximum at 530 nm to 620 nm. A method for using a photosensitive lithographic printing plate, which is performed under a light-emitting diode lamp. 6. The method of using a photosensitive lithographic printing plate according to claim 5, wherein the photosensitive layer contains at least one compound selected from a titanocene compound, an iron arene complex compound, and a biimidazole compound as a photopolymerization initiator. The method for using a photosensitive lithographic printing plate according to claim 6, wherein the photosensitive layer further contains a polyhalogen compound as a photopolymerization initiator. The method for using a photosensitive lithographic printing plate according to claim 7, wherein the polymerizable ethylenically unsaturated bond-containing compound has a tertiary amino group in the molecule. A photosensitive lithographic printing plate produced by the method of producing a photosensitive lithographic printing plate according to claim 1 is used by the method of using the photosensitive lithographic printing plate according to claim 5. How to use the plate.