JP2005114891A - Photosensitive planographic printing plate material and platemaking method for photosensitive planographic printing plate material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive planographic printing plate material having high sensitivity and excellent storage property and print durability and to provide its platemaking method. <P>SOLUTION: In the photosensitive planographic printing plate material having a photopolymerizable photosensitive layer on an aluminum substrate subjected to roughening process and anodic oxidation process, the roughening process is carried out by AC electrolysis in an electrolytic solution containing hydrochloric acid and the anodic oxidation process is carried out in an electrolytic solution containing sulfuric acid to obtain 3 to 5 g/m<SP>2</SP>deposition of the anodic oxidation film. The photopolymerizable photosensitive layer contains: (A) a photopolymerization initiator; (B) a polymer binder; (C) an addition polymerizable compound containing an ethylenically unsaturated bond; and (D) a dye expressed by general formula (1) and having an absorption maximum in the wavelength range of 380 nm to 440 nm. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a photopolymerization type photosensitive lithographic printing plate material using aluminum as a support, and a plate making method thereof, which are used in a computer-to-plate system (hereinafter referred to as CTP).

  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.

  On the other hand, in recent years, the printing industry has been screaming for environmental conservation, and printing inks that do not use petroleum-based volatile organic compounds (VOCs) have been developed and are widely used. Printing plate materials corresponding to these inks Is required.

  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, even in these printing plate materials, stains may occur during printing due to storage of the printing plate materials, and stains in shadow portions may occur when printing many sheets, and dot reproducibility may deteriorate. In particular, in the printing with the above-described de-VOC ink, these problems are remarkable, and the sensitivity, storage stability and printing durability are insufficient.
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 photosensitive lithographic printing plate material having high sensitivity and excellent storage stability and printing durability, and a plate making method thereof.

The object of the present invention is achieved by the following constitution.
(Claim 1)
In a photosensitive lithographic printing plate material having a photopolymerizable photosensitive layer on a roughened and anodized aluminum support, the roughened treatment is AC electrolyzed in an electrolyte containing hydrochloric acid. A roughening treatment, and the anodizing treatment is an anodizing treatment in which an amount of an anodized film is 3 to 5 g / m ² in an electrolyte containing sulfuric acid, and the photopolymerizable photosensitive layer is (A) Photopolymerization initiator, (B) polymer binder, (C) addition-polymerizable ethylenically unsaturated bond-containing compound, (D) represented by the following general formula (1) having an absorption maximum in the wavelength range of 380 nm to 440 nm A photosensitive lithographic printing plate material comprising a photopolymerizable photosensitive layer containing a dye to be produced.

Wherein R ^{1 to} R ⁶ are a hydrogen atom, alkyl group, alkenyl group, alkynyl group, heteroaryl group, heterocyclic group, alkoxy group, cycloalkoxy group, alkylthio group, cycloalkylthio group, arylthio group, alkoxycarbonyl A group, aryloxycarbonyl group, sulfamoyl group, acyl group, amide group, carbamoyl group, ureido group, sulfinyl group, alkylsulfonyl group, arylsulfonyl group, amino group, halogen atom, cyano group, nitro group, hydroxy group. These substituents may be further substituted with the above substituents, and a plurality of these substituents may be bonded to each other to form a ring.)
(Claim 2)
The photosensitive lithographic printing plate material according to claim 1, wherein the amount with the anodized film is 4 to 5 g / m ² .
(Claim 3)
3. The photosensitive lithographic printing plate according to claim 1, wherein the surface roughness (arithmetic mean roughness (Ra)) of the aluminum support on the photosensitive layer side is 0.4 to 0.6 [mu] m. material.
(Claim 4)
The photosensitive lithographic printing plate material according to claim 1, wherein the photopolymerization initiator (A) is an iron arene complex compound.
(Claim 5)
4. The photosensitive lithographic printing plate material according to claim 1, wherein the photopolymerization initiator (A) is a trihaloalkyl compound.
(Claim 6)
(A) The photopolymerization initiator is a trihaloalkyl compound, and the (C) addition-polymerizable ethylenically unsaturated bond-containing compound containing a group that can be oxidized by light is added. The photosensitive lithographic printing plate material according to claim 1, wherein:
(Claim 7)
7. The photosensitive lithographic printing plate material according to claim 1, wherein the aluminum support is anodized and then subjected to polyvinylphosphonic acid treatment.
(Claim 8)
An alkaline developer having a pH of 10.0 to 12.5 after image exposure of the photosensitive lithographic printing plate material according to any one of claims 1 to 7 with a laser beam having an emission wavelength in a wavelength range of 350 nm to 450 nm. A process for making a photosensitive lithographic printing plate material, characterized in that:

  The constitution of the present invention can provide a photosensitive lithographic printing plate material having high sensitivity, excellent storage stability at high humidity, and giving high-quality printed matter without causing stains when printing a large number of sheets, and a plate making method thereof. .

  Hereinafter, the present invention will be described in detail.

  The present invention is a photosensitive lithographic printing plate having a combination of a support of an aluminum plate subjected to a specific surface treatment and a specific photopolymerization type photosensitive layer, and a plate making method using the same.

(Support and surface treatment)
An aluminum plate is used as the support for the photosensitive lithographic printing plate used in the present invention. In this case, a pure aluminum plate, an aluminum alloy plate, or the like may be used.

  Various aluminum alloys can be used, for example, alloys of aluminum and metals such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, nickel, titanium, sodium, iron, etc. An aluminum plate produced by the method can be used. In addition, a recycled aluminum plate obtained by rolling recycled aluminum ingots such as scrap materials and recycled materials that are becoming popular in recent years can also be used.

  The support of the photosensitive lithographic printing plate used in the present invention is preferably subjected to a degreasing treatment in order to remove rolling oil on the surface prior to roughening (graining treatment). 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.

  Next, a roughening process is performed. In the present invention, AC electrolytic surface roughening treatment is performed in an electrolytic solution containing hydrochloric acid, but prior to that, mechanical surface roughening treatment and preliminary electrolytic surface roughening treatment mainly composed of nitric acid may be performed.

The mechanical roughening method 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.

The preliminary electrolytic surface roughening treatment mainly composed of nitric acid can be generally performed by applying a voltage in the range of 1 to 50 volts, but is preferably selected from the range of 10 to 30 volts. Current density may be in the range of 10 to 200 A / dm ^2, preferably selected from the range of 20 to 100 A / dm ^2. The quantity of electricity, may be in the range of 5000 C / dm ^2, preferably selected from the range of 100~2000c / dm ^2. The temperature at which the electrochemical roughening method is performed can be in the range of 10 to 50 ° C, but is preferably selected from the range of 15 to 45 ° C. The concentration of nitric acid in the electrolytic solution is preferably 0.1 to 5% by mass. If necessary, nitrates, chlorides, amines, aldehydes, phosphoric acid, chromic acid, boric acid, acetic acid, oxalic acid, aluminum ions, and the like can be added to the electrolytic solution.

After the preliminary electrolytic surface-roughening treatment mainly composed of nitric acid, 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.

  Next, in the present invention, an AC electrolytic surface roughening treatment is performed in an electrolytic solution containing hydrochloric acid.

The hydrochloric acid concentration is preferably 5 to 20 g / l, more preferably 6 to 15 g / l. The current density is 15 to 70 A / dm ² , preferably 20 to 65 A / dm ² . The quantity of electricity was 400~2000C / dm ^2, preferably 500~1200C / dm ^2. The frequency is preferably in the range of 40 to 150 Hz. The temperature of the electrolytic solution can be in the range of 10 to 50 ° C, but is preferably selected from the range of 15 to 45 ° C.

  If necessary, nitrates, chlorides, amines, aldehydes, phosphoric acid, chromic acid, boric acid, acetic acid, oxalic acid, aluminum ions, and the like can be added to the electrolytic solution.

After the electrolytic surface-roughening treatment is performed in the electrolytic solution containing hydrochloric acid, it is preferably immersed in an aqueous solution of acid or alkali in order to remove aluminum scraps on the surface. Examples of the acid include sulfuric acid, persulfuric acid, hydrofluoric acid, phosphoric acid, nitric acid, hydrochloric acid, and the like. Examples of the base include sodium hydroxide and potassium hydroxide. Among these, it is preferable to use an alkaline aqueous solution. The amount of aluminum dissolved on the surface is preferably 0.5 to ² g / m2. 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 roughening treatment, an anodizing treatment is performed to form an anodized film. The anodizing method used in the present invention is performed using sulfuric acid or an electrolytic solution mainly composed of sulfuric acid as the electrolytic solution. The concentration of sulfuric acid is preferably 5 to 50% by mass, particularly preferably 10 to 35% by mass. The temperature is preferably 10 to 50 ° C. The treatment voltage is preferably 18V or more, and more preferably 20V or more. Current density is preferably 1~30A / dm ^2. Quantity of electricity is preferably from 200~600C / dm ^2.

The anodic oxidation coating amount to be formed is adjusted to ³ to 5 g / m ^2, and preferably 4 to 5 g / m ² . The amount of anodic oxidation coating is, for example, by 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 layer, It is obtained from mass change measurement before and after dissolution of the coating on the plate. Micropores are generated in the anodized film, and the density of the micropores is preferably 400 to 700 / μm ^{2, and} more preferably 400 to 600 / μm ² .

  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, in the present invention, it is preferable to perform a hydrophilic treatment after performing these treatments. Hydrophilization treatment is not particularly limited, but a water-soluble resin such as polyvinylphosphonic acid, a polymer and copolymer having a sulfonic acid group in the side chain, polyacrylic acid, a water-soluble metal salt (for example, zinc borate) or Undercoat with yellow dye or amine salt can be used. Furthermore, a sol-gel treated substrate in which a functional group capable of causing an addition reaction by a radical as disclosed in JP-A-5-304358 is covalently used.

  Preferably, the support surface is hydrophilized with polyvinylphosphonic acid. The treatment is not limited to a coating method, a spray method, a dip method, or the like, but a dip method is suitable for making the equipment inexpensive. In the case of a dip type, it is preferable to treat polyvinylphosphonic acid with a 0.05 to 3% aqueous solution. The treatment temperature is preferably 20 to 90 ° C., and the treatment time is preferably 10 to 180 seconds. After the treatment, it is preferable to perform a squeegee treatment or a water washing treatment in order to remove the excessively laminated polyvinylphosphonic acid. Furthermore, it is preferable to perform a drying process. As a drying temperature, 20-95 degreeC is preferable.

  The arithmetic average roughness (Ra) of the surface on the photosensitive layer side of the obtained aluminum support is preferably 0.4 to 0.6 μm, and is controlled by a combination of hydrochloric acid concentration, current density, and electric quantity in the roughening treatment. I can do it.

(Photopolymerization initiator)
The photopolymerization initiator of the present invention is a compound capable of initiating polymerization of an (C) addition-polymerizable ethylenically unsaturated bond-containing compound by image exposure, and those that can be preferably used include titanocene compounds, monoalkyltriaryls Examples thereof include borate compounds, iron arene complex compounds, and trihaloalkyl compounds.

  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- (py-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.

  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 the present invention, an iron arene complex compound is particularly preferably used.

  Examples of the iron arene complex compound include compounds described in JP-A-59-219307. More preferred specific examples include η-benzene- (η-cyclopentadienyl) iron hexafluorophosphate, η-cumene. -(Η-cyclopentadienyl) iron hexafluorophosphate, η-fluorene- (η-cyclopentadienyl) iron hexafluorophosphate, η-naphthalene- (η-cyclopentadienyl) iron hexafluorophosphate, η- Examples include xylene- (η-cyclopentadienyl) iron hexafluorophosphate, η-benzene- (η-cyclopentadienyl) iron tetrafluoroborate.

  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: 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", 84, 85-277 (1988) ) And transition metal complexes containing a transition metal such as ruthenium described in JP-A-2-182701; 2,4,5-triarylimidazole dimer described in JP-A-3-209477; carbon tetrabromide, JP Organic halogen compounds described in JP-A-59-107344, etc.

(Trihaloalkyl compound)
The photopolymerizable photosensitive layer of the present invention preferably contains a trihaloalkyl compound. The trihaloalkyl compound is a compound having a trihaloalkyl group, particularly when an addition-polymerizable ethylenically unsaturated bond-containing compound containing a group that can be oxidized by light is included as an addition-polymerizable ethylenically unsaturated bond-containing compound. Preferably used. 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 the specifications of 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 BR66, 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.

  In the present invention, a coumarin dye represented by the general formula (1) is used as a sensitizing dye.

In the formula, R ^{1 to} R ⁶ are each a hydrogen atom, an alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group, Tetradecyl group, pentadecyl group etc.), cycloalkyl group (eg cyclopentyl group, cyclohexyl group etc.), alkenyl group (eg vinyl group, allyl group etc.), alkynyl group (eg ethynyl group, propargyl group etc.), aryl group (For example, phenyl group, naphthyl group, etc.), heteroaryl group (for example, furyl group, thienyl group, pyridyl group, pyridazyl group, pyrimidyl group, pyrazyl group, triazyl group, imidazolyl group, pyrazolyl group, thiazolyl group, benzoimidazolyl group, Benzoxazolyl group, quinazolyl group, phthalazyl group, etc.), f B-ring group (for example, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.), alkoxy group (for example, methoxy group, ethoxy group, propyloxy group, pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group) Etc.), cycloalkoxy groups (eg cyclopentyloxy group, cyclohexyloxy group etc.), aryloxy groups (eg phenoxy group, naphthyloxy group etc.), alkylthio groups (eg methylthio group, ethylthio group, propylthio group, pentylthio group) Hexylthio group, octylthio group, dodecylthio group, etc.), cycloalkylthio group (eg, cyclopentylthio group, cyclohexylthio group, etc.), arylthio group (eg, phenylthio group, naphthylthio group, etc.), alkoxycarbonyl group (example) For example, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), sulfamoyl group (For example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl Group, 2-pyridylaminosulfonyl group, etc.), acyl group (for example, acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl) Cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), acyloxy group (for example, acetyloxy group, ethylcarbonyloxy group, butylcarbonyloxy) Group, octylcarbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.), amide group (for example, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexyl) Carbonylamino group, 2-ethylhexylcarbonylamino group, octylcarbonylamino group, dodecylcarbonylamino group, phenylcarbonylamino , Naphthylcarbonylamino group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexyl) Aminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido) Group, dodecylureido group, phenylureido group, naphthylureido group, 2-pyridylaminoureido group, etc.), sulfinyl group (for example, methylsulfinyl) Group, ethylsulfinyl group, butylsulfinyl group, cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, naphthylsulfinyl group, 2-pyridylsulfinyl group, etc.), alkylsulfonyl group (for example, methylsulfonyl group, Ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, etc.), arylsulfonyl group (phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), amino group (for example, amino Group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, - pyridylamino group, etc.), a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom), a cyano group, a nitro group, hydroxy group, and the like. These substituents may be further substituted with the above substituents. In addition, a plurality of these substituents may be bonded to each other to form a ring.

Among these, particularly preferred is a coumarin having an amino group, an alkylamino group, a dialkylamino group, an arylamino group, a diarylamino group or an alkylarylamino group as R ⁵ . In this case, an alkyl group substituted with an amino group that forms a ring with the substituents R ⁴ and R ⁶ can also be preferably used.

Furthermore, either or both of R ¹ and R ² are alkyl groups (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group). Group, tetradecyl group, pentadecyl group etc.), cycloalkyl group (eg cyclopentyl group, cyclohexyl group etc.), alkenyl group (eg vinyl group, allyl group etc.), aryl group (eg phenyl group, naphthyl group etc.), Heteroaryl group (for example, furyl group, thienyl group, pyridyl group, pyridazyl group, pyrimidyl group, pyrazyl group, triazyl group, imidazolyl group, pyrazolyl group, thiazolyl group, benzoimidazolyl group, benzoxazolyl group, quinazolyl group, phthalazyl group Etc.), heterocyclic groups (eg, pyrrolidyl group, imida Lysyl group, morpholyl group, oxazolidyl group, etc.), alkoxycarbonyl group (eg, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (eg, , Phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), acyl group (for example, acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group) Phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), acyloxy group (for example, acetyloxy group, ethylcarbonyloxy group, butylcarbonyl group) Xy group, octylcarbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexyl) Aminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), sulfinyl group (for example, methylsulfinyl group, ethylsulfinyl group) Group, butylsulfinyl group, cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group Group, naphthylsulfinyl group, 2-pyridylsulfinyl group, etc.), alkylsulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, etc.), arylsulfonyl Group (phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), halogen atom (for example, fluorine atom, chlorine atom, bromine atom, etc.), cyano group, nitro group, halogenated alkyl group (trifluoromethyl group, More preferred are tribromomethyl group, trichloromethyl group and the like.

  Preferable specific examples include, but are not limited to, the following compounds.

  In addition to the above specific examples, 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, JP-A-2002-363206 No. 1 to 21 Coumarin Derivatives, JP-A No. 2002-363207 No. 1 to 40 Coumarin Derivatives, JP-A No. 2002-363208 No. 1 to 34 Coumarin Derivatives, JP-A No. 2002-363209 No. 1 56 coumarin derivatives and the like can also be preferably used.

  The amount of the coumarin dye used as the sensitizing dye of the present invention in the photosensitive layer is such that the reflection density of the printing plate at the recording light source wavelength is in the range of 0.1 to 1.2. preferable. The mass ratio of the dye in the photosensitive layer, which falls within this range, varies greatly depending on the molecular extinction coefficient of each dye and the degree of crystallinity in the photosensitive layer, but generally from 0.5% by mass. Often in the range of 10% by weight.

  Moreover, the compounding quantity of a polymerization initiator, a trihaloalkyl compound, and a sensitizing dye becomes like this. Preferably it is 0.1-20 mass parts in a photopolymerizable photosensitive layer of a photosensitive layer, Preferably it is 3-12 mass parts. The blending ratio of the photopolymerization initiator, the trihaloalkyl compound and the sensitizing dye is based on the three total amounts, the ratio of the photopolymerization initiator is 30 to 55 parts by mass, and the ratio of the trihaloalkyl compound is 3 to 15 masses. Part and the ratio of a sensitizing dye are 40-67 mass parts.

(Polymer binder)
Examples of the polymer binder used in the present invention include acrylic polymers, polyvinyl butyral resins, polyurethane resins, polyamide resins, polyester resins, epoxy resins, phenol resins, polycarbonate resins, polyvinyl butyral resins, polyvinyl formal resins, shellacs, and others. 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, in the polymer binder of 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.

  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 of 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 above-mentioned vinyl polymer having a carboxyl group and a polymerizable double bond in the side chain used in the present invention is preferably 50 to 100% by mass and 100% by mass in the total polymer binder. More preferred.

  The content of the polymer binder in the photopolymerizable photosensitive layer applied and formed as a 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 20 to 50% by mass. It is particularly preferable from the viewpoint of sensitivity to use in the above range.

(Addition-polymerizable ethylenically unsaturated bond-containing compound)
The addition-polymerizable ethylenically unsaturated bond-containing compound of the present invention is a compound having a polymerizable 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 ethylenically unsaturated 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 by replacing these acrylates with methacrylate, itaconate, crotonate, maleate Steal, 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 dimethyl Difunctional acrylic acid esters such as ε-caprolactone adduct of acrylate acrylate, diglycidyl ether of 1,6-hexanediol, or methacrylic acid, itaconic acid in which these acrylates are replaced with methacrylate, itaconate, crotonate, maleate , Crotonic acid, maleic acid esters such as trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, trimethylolethane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, di Pentaerythritol hexaacrylate, dipentaerythritol hexaacrylate Polyfunctional acrylic acid ester such as rolactone adduct, pyrogallol triacrylate, propionic acid / dipentaerythritol triacrylate, propionic acid / dipentaerythritol tetraacrylate, hydroxypivalylaldehyde-modified dimethylolpropane triacrylate, or these acrylates Examples thereof include methacrylic acid, itaconic acid, crotonic acid, and maleic acid ester instead of methacrylate, itaconate, crotonate, and maleate.

  Examples of the addition-polymerizable ethylenically unsaturated bond-containing compound used in the photopolymerizable photosensitive layer of the present invention include polyfunctional oligomers and prepolymers.

  Examples of the prepolymer include the following compounds, and a prepolymer obtained by introducing acrylic acid or methacrylic acid into an oligomer having an appropriate molecular weight to impart photopolymerizability can also 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 Acrylates; for example, epoxy acrylates in which (meth) acrylic acid is introduced into an epoxy resin such as bisphenol A, epichlorohydrin, (meth) acrylic acid, phenol novolac, epichlorohydrin, (meth) acrylic acid; 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 resins; for example, silicone resin acrylates such as polysiloxane acrylate, polysiloxane diisocyanate, 2-hydroxyethyl acrylate; and (meth) acryloyl in oil-modified alkyd resins Examples include prepolymers such as alkyd-modified acrylates and spirane resin acrylates having a group introduced therein.

  The unsaturated bond-containing compound according to the present invention used in the photopolymerizable photosensitive layer of the present invention includes phosphazene monomer, triethylene glycol, isocyanuric acid EO (ethylene oxide) -modified diacrylate, isocyanuric acid EO-modified triacrylate. , Dimethylol tricyclodecane diacrylate, trimethylol propane acrylic acid benzoate, alkylene glycol type acrylic acid modified / urethane modified acrylate and other monomers, and addition polymerizable compounds having structural units formed from the monomers Mention may be made of oligomers and prepolymers.

  Furthermore, examples of the unsaturated group-containing compound according to the present invention used in the photopolymerizable photosensitive layer of the present invention include a phosphate ester compound 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- No. 67189, JP-A-1-244891, and the like. Furthermore, “11290 Chemical Products”, Chemical Industry Daily, p. 286-p. 294, “UV / EB Curing Handbook (raw material)”, Kobunshi Shuppankai, 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.

(Addition polymerizable ethylenically unsaturated bond-containing monomer containing a group that can be oxidized by light)
The addition-polymerizable ethylenically unsaturated bond-containing compound used in the photopolymerizable photosensitive layer of the present invention is an addition-polymerizable ethylenically unsaturated bond-containing compound containing at least one group that can be oxidized by light. Is preferred.

  Particularly preferred are addition polymerizable compounds containing at least one photooxidizable group and at least one urethane group in the molecule. Suitable photooxidizable groups are in particular thio groups, thioether groups, ureido groups, amino groups and enol groups which may be members of the heterocyclic ring. Examples of these groups are triethanolamino group, triphenylamino group, thioureido group, imidazolyl group, oxazolyl group, thiazolyl group, acetylacetonyl residue, N-phenylglycine residue and ascorbic acid residue. Preference is given to addition-polymerizable compounds containing a tertiary amino group and a thioether group.

  Examples of the compound containing a photooxidizable group are described in European Patent Publication Nos. 287,818, 353,389 and 364,735. Preferred among the compounds described therein are those containing a ureido group and / or a urethane group in addition to the tertiary amino group.

  Examples of the compound having at least one photooxidizable group and at least one urethane group of the present invention include JP-A 63-260909, JP-A 2669849, JP-A 6-35189, JP-A 2001-2001. The thing of 125255 is mentioned.

  Furthermore, the present invention uses 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. Is preferred.

  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, 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. Although it does not specifically limit as a compound containing the ethylenic double bond which can be addition-polymerized with a hydroxyl group in a molecule | numerator, Preferably, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, 2- Examples include hydroxypropylene-1,3-dimethacrylate and 2-hydroxypropylene-1-methacrylate-3-acrylate.

  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.

(Other addition-polymerizable ethylenically unsaturated bond-containing compounds)
The addition-polymerizable ethylenically unsaturated bond-containing compound used in the photopolymerizable photosensitive layer of the present invention can be used in combination with radically polymerizable monomers, polyfunctional oligomers, prepolymers and the like other than those described above.

  Examples of the prepolymer include the following compounds, and a prepolymer obtained by introducing acrylic acid or methacrylic acid into an oligomer having an appropriate molecular weight to impart photopolymerizability can also 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 Acrylates; for example, epoxy acrylates in which (meth) acrylic acid is introduced into an epoxy resin such as bisphenol A, epichlorohydrin, (meth) acrylic acid, phenol novolac, epichlorohydrin, (meth) acrylic acid; 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 resins; for example, silicone resin acrylates such as polysiloxane acrylate, polysiloxane diisocyanate, 2-hydroxyethyl acrylate; and (meth) acryloyl in oil-modified alkyd resins Examples include prepolymers such as alkyd-modified acrylates and spirane resin acrylates having a group introduced therein.

  The unsaturated bond-containing compound according to the present invention used in the photopolymerizable photosensitive layer of the present invention includes phosphazene monomer, triethylene glycol, isocyanuric acid EO (ethylene oxide) -modified diacrylate, isocyanuric acid EO-modified triacrylate. , Dimethylol tricyclodecane diacrylate, trimethylol propane acrylic acid benzoate, alkylene glycol type acrylic acid modified / urethane modified acrylate and other monomers, and addition polymerizable compounds having structural units formed from the monomers Mention may be made of oligomers and prepolymers.

  Furthermore, examples of the unsaturated group-containing compound according to the present invention used in the photopolymerizable photosensitive layer of the present invention include a phosphate ester compound 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- No. 67189, JP-A-1-244891, and the like. Furthermore, “11290 Chemical Products”, Chemical Industry Daily, p. 286-p. 294, “UV / EB Curing Handbook (raw material)”, Kobunshi Shuppankai, 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.

  The photosensitive lithographic printing plate material of the present invention contains the above-described addition-polymerizable ethylenically unsaturated bond-containing compound according to the present invention in the range of 1.0 to 80.0% by mass of the photosensitive layer. More preferably, it is the range of 3.0-70.0 mass%.

(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-t-butylphenol), N-nitrosophenylhydroxylamine primary cerium salt, 2,2,6,6-tetramethylpiperidine derivatives, 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. 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 addition to the components described above, a colorant can also be used in the photopolymerizable photosensitive layer of the present invention, and 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.

(Application)
Examples of the solvent used in preparing the coating composition for the photopolymerizable photosensitive layer of the present invention include alcohols: sec-butanol, isobutanol, n-hexanol, benzyl alcohol, diethylene glycol, triethylene glycol, Tetraethylene glycol, 1,5-pentanediol, etc .; ethers: propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, etc .; ketones, aldehydes: diacetone alcohol, cyclohexanone, methylcyclohexanone, etc .; esters Preferred examples include: ethyl lactate, butyl lactate, diethyl oxalate, methyl benzoate and the like.

  The prepared coating composition (photosensitive layer coating solution) can be coated on a support by a conventionally known method and dried to produce a photopolymerizable 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. Can be mentioned.

  The drying temperature of the photosensitive layer is preferably in the range of 60 to 160 ° C, more preferably 80 to 140 ° C, and particularly preferably 90 to 120 ° C.

(Protective layer)
It is preferable to provide a protective layer on the upper side of the photopolymerizable photosensitive layer of the present invention. The protective layer (oxygen barrier layer) is preferably highly soluble in a developer (generally an alkaline aqueous solution).

  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 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, the known coating methods mentioned above for coating 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.

(Plate making method-Image exposure)
In the present invention, the photosensitive lithographic printing plate is exposed with a laser in the ultraviolet region of 350 nm to 450 nm. The following can be used as an available laser light source having a wavelength of 350 to 450 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 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.

(Heat treatment)
In the present invention, after the image exposure, a heat treatment may be performed to accelerate the image formation reaction and improve the sensitivity and printing durability. The method of the heat treatment is not particularly limited, but a non-contact method to the image forming surface is preferable, and a commercially available automatic processor equipped with a normal thermostatic bath, a hot air dryer and a heat treatment unit can be used. The heating temperature is preferably 100 to 130 ° C. at the plate surface temperature.

(developing)
In the present invention, the photosensitive lithographic printing plate subjected to image exposure is developed with a known developer containing water, salts, alkali agents, acids, surfactants, solvents, development stabilizers, and the like. It is preferable to develop with 0-12.5 alkaline developing solution.

(Alkaline agent)
The main component of the developer and its replenisher used in the present invention preferably contains at least one compound selected from silicic acid, phosphoric acid, carbonic acid, boric acid, phenols, saccharides, oximes and fluorinated alcohols. An alkaline aqueous solution having a pH higher than 8.5 and lower than 13.0 is preferable. More preferably, the pH is 10 to 12.5. Among these, as weakly acidic substances such as phenols, saccharides, oximes and fluorinated alcohols, those having a dissociation index (pKa) of 10.0 to 13.2 are preferable. Such an acid is selected from those described in IONISATION CONSTANTS OF ORGANIC ACIDS INAQUEOUS SOLUTION published by PergamonPress, and specifically, salicylic acid (13.0) and 3-hydroxy-2-naphthoic acid. (Same as 12.84), catechol (12.6), gallic acid (12.4), sulfosalicylic acid (11.7), 3,4-dihydroxysulfonic acid (12.2), 3,4 -Dihydroxybenzoic acid (11.94), 1,2,4-trihydroxybenzene (11.82), hydroquinone (11.56), pyrogallol (11.34), o-cresol (10. 33), resorsonol (same as 11.27), p-cresol (same as 10.27), and phenols having a phenolic hydroxyl group such as m-cresol (10.09).

  As the saccharide, a non-reducing sugar that is stable even in an alkali is preferably used. Such non-reducing sugars are saccharides that do not have a free aldehyde group or ketone group and do not exhibit reducing properties, and are trehalose-type oligosaccharides in which reducing groups are bonded to each other, and glycosides in which a reducing group of saccharides and non-saccharides are bonded. These are classified into sugar alcohols reduced by hydrogenation of the body and saccharides, both of which are preferably used in the present invention. Trehalose type oligosaccharides include saccharose and trehalose. Examples of glycosides include alkyl glycosides, phenol glycosides, mustard oil glycosides, and the like. Examples of the sugar alcohol include D, L-arabit, rebit, xylit, D, L-sorbit, D, L-mannit, D, L-exit, D, L-talit, durisit and allozulcit. Furthermore, maltitol obtained by hydrogenation of a disaccharide and a reduced form (reduced water candy) obtained by hydrogenation of an oligosaccharide are preferably used. Furthermore, 2-butanone oxime (12.45), acetoxime (12.42), 1.2-cycloheptanedione oxime (12.3), 2-hydroxybenzaldehyde oxime (12.10), dimethyl Oximes such as glyoxime (11.9), ethanediamide dioxime (11.37) and acetophenone oxime (11.35) such as 2,2,3,3-tetrafluoropropanol-1 (12) .74), trifluoroethanol (12.37), trichloroethanol (12.24), and the like. In addition, aldehydes such as pyridine-2-aldehyde (12.68) and pyridine-4-aldehyde (12.05), adenosine (12.56), inosine (12.5), guanine ( 12.3), nucleic acid-related substances such as cytosine (12.2), hypoxanthine (12.1), xanthine (11.9), diethylaminomethylsulfonic acid (12.32), 1-amino-3,3,3-trifluorobenzoic acid (12.29), isopropylidenedisulfonic acid (12.10), 1,1-ethylidene diphosphonic acid (11.54), 1,1 -1-hydroxyethylidene disulfonate (11.52), benzimidazole (12.86), thiobenzamide (12.8), picolinethioamide (12.55), barbi Include weak acid, such as Le acid (same 12.5). These acidic substances may be used alone or in combination of two or more. Among these acidic substances, preferred are silicic acid, phosphoric acid, carbonic acid, sulfosalicylic acid, salicylic acid and sugar alcohols and saccharose of non-reducing sugars, especially silicic acid, D-sorbitol, saccharose, and reduced water candy in an appropriate pH range. It is preferable that it has a buffering action and is inexpensive.

  The proportion of these acidic substances in the developer is preferably from 0.1 to 30% by mass, and more preferably from 1 to 20% by mass.

Other examples include potassium silicate, sodium silicate, lithium silicate, ammonium silicate, potassium metasilicate, sodium metasilicate, lithium metasilicate, ammonium metasilicate, tripotassium phosphate, trisodium phosphate, trilithium phosphate, triammonium phosphate, phosphoric acid. Dipotassium, disodium phosphate, dilithium phosphate, diammonium phosphate, potassium carbonate, sodium carbonate, lithium carbonate, ammonium carbonate, potassium bicarbonate, sodium bicarbonate, lithium bicarbonate, ammonium bicarbonate, potassium borate, sodium borate, boric acid Lithium, ammonium borate and the like can be mentioned and may be added in the form of a preformed salt. Again, sodium hydroxide, ammonium, potassium and lithium can be added to the pH adjustment. Moreover, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, Organic alkali agents such as ethyleneimine, ethylenediamine, and pyridine are also used in combination. Most preferred are potassium silicate and sodium silicate. The concentration of silicate is preferably 1.0 to 3.0% by mass in terms of SiO ₂ concentration. Further, SiO ₂ and mol ratio of the alkali metal M (SiO ₂ / M) is still preferably be in the range of 0.25 to 2.

  The developing solution referred to in the present invention is not only an unused solution used at the start of development, but also a replenishing solution is replenished to correct the activity of the solution that is lowered by processing, and the activity is maintained. Liquid (so-called running liquid). The replenisher therefore needs to have a higher activity (alkali concentration) than the developer, so the pH of the replenisher may exceed 13.0.

(Surfactant)
To the developer and replenisher used in the present invention, various surfactants and organic solvents can be added as necessary for the purpose of promoting developability, dispersing development residue, and improving ink affinity of the printing plate image area. Preferred surfactants include anionic, cationic, nonionic and amphoteric surfactants. Preferred examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, ester polyoxyethylene alkyl phenyl ethers, polyoxyethylene naphthyl ethers, polyoxyethylene polystyryl phenyl ethers, polyoxyethylene poly ethers. Oxypropylene alkyl ethers, glycerin fatty acid partial esters, sorbitan fatty acid partial esters, pentaerythritol fatty acid partial esters, propylene glycol mono fatty acid esters, sucrose fatty acid partial esters, polyoxyethylene sorbitan fatty acid partial esters, polyoxyethylene Sorbitol fatty acid partial esters, polyethylene glycol fatty acid esters, polyglycerin fatty acid partial esters, polyoxy Ethyleneated castor oil, polyoxyethylene glycerin fatty acid partial ester, polyoxyethylene-polyoxypropylene block copolymer, polyoxyethylene-polyoxypropylene block copolymer adduct of ethylenediamine, fatty acid diethanolamides, N, N -Nonionic surfactants such as bis-2-hydroxyalkylamines, polyoxyethylene alkylamines, triethanolamine fatty acid esters, trialkylamine oxides, fatty acid salts, abietic acid salts, hydroxyalkane sulfonates, alkane sulfones Acid salts, dialkylsulfosuccinic acid ester salts, linear alkylbenzene sulfonates, branched alkylbenzene sulfonates, alkylnaphthalene sulfonates, polyoxyethylene aliquots Ether carboxylic acid, polyoxyethylene naphthyl ether sulfate, alkyl diphenyl ether sulfonate, alkylphenoxy polyoxyethylene propyl sulfonate, polyoxyethylene alkyl sulfophenyl ether, polyoxyethylene aryl ether sulfate, N-methyl -N-oleyl taurine sodium salt, N-alkylsulfosuccinic acid monoamide disodium salt, petroleum sulfonates, sulfated tallow oil, fatty acid alkyl ester sulfate ester salt, alkyl sulfate ester salt, polyoxyethylene alkyl ether sulfate ester salt , Fatty acid monoglyceride sulfates, polyoxyethylene alkylphenyl ether sulfates, polyoxyethylene styrylphenyl ether Tellurium sulfate ester salt, alkyl phosphate ester salt, polyoxyethylene alkyl ether phosphate ester salt, polyoxyethylene alkyl phenyl ether phosphate ester salt, partially saponified styrene / maleic anhydride copolymer, olefin / maleic anhydride Anionic surfactants such as partially saponified acid copolymers, naphthalenesulfonate formalin condensates, alkylamine salts, quaternary ammonium salts such as tetrabutylammonium bromide, polyoxyethylene alkylamine salts, polyethylene polyamine Examples include cationic surfactants such as derivatives, and amphoteric surfactants such as carboxybetaines, aminocarboxylic acids, sulfobetaines, aminosulfuric esters, and imidazolines. Among the surfactants listed above, those having polyoxyethylene can be read as polyoxyalkylenes such as polyoxymethylene, polyoxypropylene and polyoxybutylene, and these surfactants are also included. A more preferred surfactant is a fluorosurfactant containing a perfluoroalkyl group in the molecule. Such fluorosurfactants include perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, anionic types such as perfluoroalkyl phosphates, amphoteric types such as perfluoroalkyl betaines, and perfluoroalkyltrimethylammonium salts. Cationic and perfluoroalkylamine oxides, perfluoroalkyl ethylene oxide adducts, perfluoroalkyl group and hydrophilic group-containing oligomers, perfluoroalkyl group and lipophilic group-containing oligomers, perfluoroalkyl groups, hydrophilic groups and lipophilic groups Nonionic types such as group-containing oligomers, perfluoroalkyl groups, and lipophilic group-containing urethanes can be mentioned. Said surfactant can be used individually or in combination of 2 or more types, and is added in 0.001-10 mass% in a developing solution, More preferably, it is added in 0.01-5 mass%.

(Development stabilizer)
For the developer and replenisher used in the present invention, various development stabilizers are preferably used. Preferred examples thereof include polyethylene glycol adducts of sugar alcohols described in JP-A-6-282079, tetraalkylammonium salts such as tetrabutylammonium hydroxide, phosphonium salts such as tetrabutylphosphonium bromide, and iodonium such as diphenyliodonium chloride. A salt is a preferred example. Further, anionic surfactants or amphoteric surfactants described in JP-A-50-51324, water-soluble cationic polymers described in JP-A-55-95946, and JP-A-56-142528 are described. There are water-soluble amphoteric polyelectrolytes that have been described. Furthermore, an organic boron compound to which an alkylene glycol is added as described in JP-A-59-84241, a polyoxyethylene / polyoxypropylene block polymerization type water-soluble surfactant as described in JP-A-60-111246, An alkylenediamine compound substituted with polyoxyethylene / polyoxypropylene disclosed in JP-A-60-129750, a polyethylene glycol having a weight average molecular weight of 300 or more described in JP-A-61-215554, and a cation described in JP-A-63-175858 And a water-soluble ethylene oxide addition compound obtained by adding 4 mol or more of ethylene oxide to an acid or alcohol disclosed in JP-A-2-39157, a water-soluble polyalkylene compound, and the like.

(Organic solvent)
If necessary, an organic solvent is added to the developer and the development replenisher. As such an organic solvent, those having a solubility in water of about 10% by mass or less are suitable, and are preferably selected from those having 5% by mass or less. For example, 1-phenylethanol, 2-phenylethanol, 3-phenyl-1-propanol, 4-phenyl-1-butanol, 4-phenyl-2-butanol, 2-phenyl-1-butanol, 2-phenoxyethanol, 2- Benzyloxyethanol, o-methoxybenzyl alcohol, m-methoxybenzyl alcohol, p-methoxybenzyl alcohol, benzyl alcohol, cyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol and 4-methylcyclohexanol, N-phenylethanol Examples thereof include amines and N-phenyldiethanolamine. The content of the organic solvent is 0.1 to 5% by mass with respect to the total mass of the liquid used, but it is preferably substantially not contained, and particularly preferably not contained at all. Here, “substantially not contained” means 1% by mass or less.

(Reducing agent)
A reducing agent is added to the developer and replenisher used in the present invention as necessary. This is to prevent stains on the printing plate. Preferable organic reducing agents include phenol compounds such as thiosalicylic acid, hydroquinone, metol, methoxyquinone, resorcin, and 2-methylresorcin, and amine compounds such as phenylenediamine and phenylhydrazine. More preferable inorganic reducing agents include sodium, potassium and ammonium salts of inorganic acids such as sulfurous acid, bisulfite, phosphorous acid, hydrogen phosphite, dihydrogen phosphite, thiosulfuric acid and dithionite. A salt etc. can be mentioned. Among these reducing agents, sulfites are particularly excellent in the antifouling effect. These reducing agents are preferably contained in the range of 0.05 to 5% by mass with respect to the developing solution at the time of use.

(Organic carboxylic acid)
If necessary, an organic carboxylic acid can be further added to the developer and replenisher used in the present invention. Preferred organic carboxylic acids are aliphatic carboxylic acids and aromatic carboxylic acids having 6 to 20 carbon atoms. Specific examples of the aliphatic carboxylic acid include caproic acid, enanthylic acid, caprylic acid, lauric acid, myristic acid, palmitic acid and stearic acid, and particularly preferred are alkanoic acids having 8 to 12 carbon atoms. . Further, it may be an unsaturated fatty acid having a double bond in the carbon chain or a branched carbon chain. Aromatic carboxylic acids are compounds in which a carboxyl group is substituted on a benzene ring, naphthalene ring, anthracene ring, etc., specifically, o-chlorobenzoic acid, p-chlorobenzoic acid, o-hydroxybenzoic acid, p- Hydroxybenzoic acid, o-aminobenzoic acid, p-aminobenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 3, There are 5-dihydroxybenzoic acid, gallic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 2-hydroxy-1-naphthoic acid, 1-naphthoic acid, 2-naphthoic acid and the like. Naphthoic acid is particularly effective. The aliphatic and aromatic carboxylic acids are preferably used as sodium salts, potassium salts or ammonium salts in order to enhance water solubility. The content of the organic carboxylic acid in the developer used in the present invention is not particularly limited, but if it is less than 0.1% by mass, the effect is not sufficient, and if it is 10% by mass or more, the effect cannot be further improved. In addition, dissolution may be hindered when other additives are used in combination. Therefore, the preferable addition amount is 0.1 to 10% by mass, more preferably 0.5 to 4% by mass with respect to the developing solution at the time of use.

(Other)
In addition to the above, the following additives can be added to the developer and replenisher used in the present invention in order to improve the development performance. For example, neutral salts such as NaCl, KCl and KBr described in JP-A-58-75152, complexes such as [Co (NH ³ )] 6Cl3 described in JP-A-59-121336, JP-A-56-142258 Amphoteric polymer electrolytes such as vinylbenzyltrimethylammonium chloride and sodium acrylate copolymer described in JP-A No. 59-75255, organometallic surfactants containing Si, Ti, etc. described in JP-A-59-75255, JP-A-59 And organic boron compounds described in Japanese Patent No. -84241. The developer and replenisher used in the present invention may further contain a preservative, a colorant, a thickener, an antifoaming agent, a hard water softener, and the like, if necessary. Examples of the antifoaming agent include mineral oil, vegetable oil, alcohol, surfactant, silicone and the like described in JP-A-2-244143. Examples of the water softener include polyphosphoric acid and its sodium salt, potassium salt and ammonium salt, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminedisuccinic acid, methyliminodiacetic acid, β-alaninediacetic acid, triethylenetetraminehexaacetic acid, hydroxyethylethylenediaminetrimethyl. Aminopolycarboxylic acids such as acetic acid, nitrilotriacetic acid, 1,2-diaminocyclohexanetetraacetic acid and 1,3-diamino-2-propanoltetraacetic acid and their sodium, potassium and ammonium salts, aminotri (methylenephosphonic acid), Ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), triethylenetetraminehexa (methylenephosphonic acid) Hydroxyethyl ethylene diamine tri (methylene phosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid and their sodium salts, potassium salts and ammonium salts. The optimum value of such a hard water softening agent varies depending on its chelating power, the hardness of the hard water used and the amount of hard water. % By mass, more preferably in the range of 0.01 to 0.5% by mass. If the addition amount is less than this range, the intended purpose is not sufficiently achieved. If the addition amount is more than this range, adverse effects on the image area such as color loss will occur. The remaining component of the developer and replenisher is water. The conductivity of the obtained developer is more preferably in the range of 5 to 50 mS.

(Concentrated liquid)
It is advantageous in terms of transportation that the developer and replenisher used in the present invention are concentrated solutions in which the water content is less than in use, and diluted with water during use. The degree of concentration in this case is appropriate so that each component does not separate or precipitate, but it is preferable to add a solubilizing agent if necessary. As such a solubilizer, a so-called hydrotrope such as toluenesulfonic acid, xylenesulfonic acid and alkali metal salts thereof described in JP-A-6-32081 is preferably used.

  The content of water in the concentrate can be further reduced to form a solid or paste. In this case, the developer may be once evaporated and then evaporated to dryness, but it is preferable that the concentrated state is obtained by mixing the materials without adding water when adding a plurality of materials or by adding a small amount of water. Is preferred. Further, this developer concentrate is disclosed in JP-A-51-61837, JP-A-2-109042, JP-A-2-109043, JP-A-3-39735, JP-A-5-142786, JP-A-6-266062, JP-A-7-2 Granules and tablets can be obtained by a conventionally well-known method described in US Pat. As the material contained in the solid or paste developer concentrate, the components used in the developer of ordinary photopolymerizable photosensitive lithographic printing plates can be used, but even if diluted with water, It is preferable not to include anything that does not return. For example, since silicate is converted into stone when it becomes low in moisture, it becomes difficult to dissolve in water, and therefore it is preferable to contain carbonate, phosphate, organic acid salt, etc. described later instead of silicate.

  These developer concentrates or solid or paste concentrates may be divided into a plurality of parts having different material types, material mixing ratios, and the like. These concentrated developer concentrates are preferably used for development after dilution to a predetermined concentration with water before development. In addition, when this developer concentrate or concentrate is used as a developer replenisher, it is most preferable to dilute with water to a predetermined concentration and then add it to the developer in use. It is also possible to put it in a developing solution as it is without diluting to a predetermined concentration. When adding the developer concentrate to a developing solution in use at a concentration higher than a predetermined concentration or without diluting to a predetermined concentration, water is added directly to the developing solution in use at the same timing or at another timing. May be added.

(Automatic processor)
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. Preferably, a mechanism for rubbing the plate surface with a roller-like brush is provided. Moreover, water etc. are used as this pretreatment liquid.

(Post-processing)
The developed plate is subjected to post-processing with a washing water, a rinse solution containing a surfactant, a finisher mainly composed of gum arabic or starch derivatives, or a protective gum solution. For the post-treatment of the PS plate of the present invention, these treatments can be used in various combinations. For example, a post-development → water wash → surfactant-containing rinse solution treatment or development → water wash → finisher solution treatment is a rinse solution. And less finisher fluid fatigue. Furthermore, a countercurrent multistage process using a rinse liquid or a finisher liquid is also a preferred embodiment.

  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 treatment method in which treatment is performed with a substantially unused post-treatment liquid can 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.

(Gum solution)
It is preferable to add an acid or a buffering agent to the gum solution in order to remove alkali components from the developer, and in addition, a hydrophilic polymer compound, a chelating agent, a lubricant, a preservative, a solubilizing agent, and the like can be added. When the gum solution contains a hydrophilic polymer compound, it also has a function as a protective agent for preventing scratches and stains on the developed plate.

(Washing water before development)
The cleaning solution used in the cleaning step before development is usually water, but various additives can be added as necessary.

  The development treatment may be performed immediately after completion of the pre-development washing step, or the development treatment may be carried out after drying after the pre-development washing step. After the development step, known post-treatments such as washing with water, rinsing and gumming can be performed.

(printing)
The photopolymerizable photosensitive plate making printing plate of the present invention is subjected to printing after plate making.

  In recent years, the printing industry has been screaming for environmental conservation, and in printing inks, inks that do not use petroleum-based volatile organic compounds (VOC) have been developed and are becoming popular. This is particularly noticeable when the printing inks are used. Examples of environmentally friendly printing inks include soybean oil ink “Naturalis 100” manufactured by Dainippon Ink & Chemicals, Inc., VOC zero ink “TK Hi-Echo NV” manufactured by Toyo Ink, and process ink “Soyselbo” manufactured by Tokyo Ink. It is done.

  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
(Synthesis of polymer binder B-1)
In a three-necked flask under a nitrogen stream, methyl methacrylate (125 parts: 1.25 mol), ethyl methacrylate (12 parts: 0.10 mol), methacrylic acid (63 parts: 0.73 mol), cyclohexanone (240 parts), Isopropyl alcohol (160 parts) and α, α′-azobisisobutyronitrile (5 parts) were added and reacted in an oil bath at 80 ° C. in a nitrogen stream for 6 hours to obtain a polymer. Thereafter, 4 parts of triethylbenzylammonium chloride and glycidyl methacrylate (52 parts: 0.73 mol) were added to the polymer and reacted at a temperature of 25 ° C. for 3 hours to obtain a polymer binder B-1. The weight average molecular weight was about 55,000 (GPC: polystyrene conversion).

(Production of support)
An aluminum plate (material 1050, tempered H16) having a thickness of 0.3 mm was immersed in a 5% aqueous sodium hydroxide solution maintained at 65 ° C., degreased for 1 minute, and then washed with water. This degreased aluminum plate was neutralized by immersing it in a 10% sulfuric acid aqueous solution maintained at 25 ° C. for 1 minute, and then washed with water. Next, this aluminum plate was subjected to an electrolytic surface roughening treatment under the conditions shown in Table 1. After electrolytic surface roughening, it was washed with water, desmutted for 10 seconds in a 1% aqueous sodium hydroxide solution maintained at 50 ° C., washed with water, and then washed in 30% sulfuric acid maintained at 50 ° C. for 30 seconds. Neutralization treatment was performed and washed with water.

  Next, anodizing treatment was performed under the conditions shown in Table 1, and washed with water. Further, a 0.44% polyvinyl phosphonic acid aqueous solution was subjected to dip treatment at 75 ° C. for 30 seconds, then washed with distilled water and dried with cold air at 25 ° C., and photosensitive lithographic printing plate supports A to T were obtained. Obtained.

(Preparation of photosensitive lithographic printing plate material)
On the surface-treated support, a photopolymerizable photosensitive layer coating solution having the following composition was coated with a wire bar so as to be 1.5 g / m ² when dried, and dried at 95 ° C. for 1.5 minutes. Thereafter, a protective layer coating solution having the following composition is further coated on the photosensitive layer with an applicator so as to be 2.0 g / m ² when dried, and dried at 75 ° C. for 1.5 minutes to protect the photosensitive layer. Photosensitive lithographic printing plate materials 1 to 60 having layers were prepared.

(Photopolymerizable photosensitive layer coating solution)
Polymer binder B-1 40.0 parts Photopolymerization initiator η-cumene- (η-cyclopentadienyl) iron hexafluorophosphate 3.0 parts Sensitizing dye (described in Table 2) 4.0 parts addition polymerization Possible ethylenically unsaturated double bond-containing compound M-3 (above)
40.0 parts addition-polymerizable ethylenically unsaturated double bond-containing monomer NK ester 4G (polyethylene glycol dimethacrylate manufactured by Shin-Nakamura Chemical Co., Ltd.)
15.0 parts hindered amine compound (LS-770: manufactured by Sankyo Co., Ltd.) 0.1 part trihaloalkyl compound (BR-41) 5.0 parts phthalocyanine pigment (MHI 454: manufactured by Gokoku Dye Co., Ltd.) 7.0 parts fluorinated surfactant Agent (F178K: manufactured by Dainippon Ink & Chemicals, Inc.) 0.5 parts methyl ethyl ketone 80 parts cyclohexanone 820 parts (protective layer coating solution)
Polyvinyl alcohol (GL-05: Nippon Synthetic Chemical Co., Ltd.) 89 parts Water-soluble polyamide (P-70: Toray Industries, Inc.) 10 parts Surfactant (Surfinol 465: Nissin Chemical Industry Co., Ltd.) 0.5 parts Water 900 (Image formation)
The photosensitive lithographic printing plate material produced in this way was 2400 dpi (2.54 cm for dpi) using a plate setter (Tiger Cat: modified product manufactured by ECRM) equipped with a light source equipped with a laser of 408 nm and 30 mW output. Image exposure was performed at a resolution of (representing the number of dots per hit). Next, before development, a heating device part, a pre-washing part for removing the protective layer, a developing part filled with the following developer composition, a washing part for removing the developer adhering to the plate surface, a gum solution for protecting the image line part ( Development processing was performed with a CTP automatic developing machine (PHW23-V: manufactured by Technigraph) equipped with GW-3: manufactured by Mitsubishi Chemical Co., Ltd. twice to obtain lithographic printing plate materials 1-60. At this time, the heating unit was set so that the plate surface temperature was 115 ° C. and the plate staying time was 15 seconds. The plate was inserted into the heating unit of the self-machine after the exposure was completed within 30 seconds.

Developer composition (aqueous solution containing the following additives)
Potassium silicate aqueous solution (SiO ₂ : 26%, K ₂ O: 13.5%) 40.0 g / L
Potassium hydroxide 4.0g / L
Ethylenediaminetetraacetic acid 0.5g / L
Polyoxyethylene (13) naphthyl ether sulfonate 20.0 g / L
1 L with water. The pH was 12.3.

(sensitivity)
A lithographic printing plate material is produced by exposing and developing a 175 line image on a photosensitive lithographic printing plate material, and the minimum amount of exposure energy at which no film reduction is observed in the 100% image portion recorded on the plate surface of the lithographic printing plate 2 times the recording energy and used as an index of sensitivity. The smaller the recording energy, the higher the sensitivity.

(Print life)
A lithographic printing plate produced by exposing and developing an image of 175 lines on a photosensitive lithographic printing plate material at 50 μJ / cm ² , coated paper, printing ink (soybean oil) with a printing machine (DAIYA1F-1: manufactured by Mitsubishi Heavy Industries). Ink Naturalis 100: manufactured by Dainippon Ink & Chemicals, Inc.) and fountain solution (H liquid SG-51 concentration 1.5%: manufactured by Tokyo Ink Co., Ltd.) are printed, and the highlight portion is thinned, the shadow portion. The number of printed sheets in which the entanglement occurs is shown as an index indicating printing durability. The larger the number of printed sheets, the higher the printing durability.

(Anti-stain properties)
Printing was performed under the same conditions as described above, and 2000 sheets were printed from the start. Thereafter, the plate was left idle for 3 minutes, and the dampening solution on the plate surface was completely dried, and then the ink application roller was brought into contact with the plate surface for 5 rotations to adhere ink to the entire plate surface. The number of printed sheets from the start of printing until the stain on the non-image area is recovered from the state of the entire background stain is shown as an index for stain prevention. It means that the one with a small number of recovered sheets is good.

(Storability)
The above evaluation was performed for a sample stored for 3 days under conditions of 23 ° C. and a relative humidity of 30% under a normal temperature environment and 55 ° C. and a relative humidity of 30% H under a high temperature environment. It was used as an index. The smaller the performance variation, the better the storage stability.

(Dirt when imprinting / halftone dot reproducibility)
Sampling was performed after printing 2000 sheets under the same printing conditions as above. Further, after printing 50000 sheets, printing was stopped and left for 1 hour, after which printing was resumed and sampled. The stain state of the non-enlarged area after printing 50000 sheets and the halftone dot reproduction area before and after printing were compared, and used as an index of stain prevention / halftone dot reproducibility during printing. It indicates that the better the smaller the fluctuation in the halftone dot reproducibility, the less the non-enlarged portion is stained.

  The results are shown in Table 2. From Table 2, according to the present invention, it is possible to provide a printed matter excellent in halftone dot reproducibility while maintaining high sensitivity, without causing stains after storage under high humidity, and without causing stains when printing many sheets. I understand.

Claims (8)

In a photosensitive lithographic printing plate material having a photopolymerizable photosensitive layer on a roughened and anodized aluminum support, the roughened treatment is AC electrolyzed in an electrolyte containing hydrochloric acid. A roughening treatment, and the anodizing treatment is an anodizing treatment in which an amount of an anodized film is 3 to 5 g / m ² in an electrolyte containing sulfuric acid, and the photopolymerizable photosensitive layer is (A) Photopolymerization initiator, (B) polymer binder, (C) addition-polymerizable ethylenically unsaturated bond-containing compound, (D) represented by the following general formula (1) having an absorption maximum in the wavelength range of 380 nm to 440 nm A photosensitive lithographic printing plate material comprising a photopolymerizable photosensitive layer containing a dye to be produced.

Wherein R ^{1 to} R ⁶ are a hydrogen atom, alkyl group, alkenyl group, alkynyl group, heteroaryl group, heterocyclic group, alkoxy group, cycloalkoxy group, alkylthio group, cycloalkylthio group, arylthio group, alkoxycarbonyl A group, aryloxycarbonyl group, sulfamoyl group, acyl group, amide group, carbamoyl group, ureido group, sulfinyl group, alkylsulfonyl group, arylsulfonyl group, amino group, halogen atom, cyano group, nitro group, hydroxy group. These substituents may be further substituted with the above substituents, and a plurality of these substituents may be bonded to each other to form a ring.) The photosensitive lithographic printing plate material according to claim 1, wherein the amount with the anodized film is 4 to 5 g / m ² . 3. The photosensitive lithographic printing plate according to claim 1, wherein the surface roughness (arithmetic mean roughness (Ra)) of the aluminum support on the photosensitive layer side is 0.4 to 0.6 [mu] m. material. The photosensitive lithographic printing plate material according to claim 1, wherein the photopolymerization initiator (A) is an iron arene complex compound. 4. The photosensitive lithographic printing plate material according to claim 1, wherein the photopolymerization initiator (A) is a trihaloalkyl compound. (A) The photopolymerization initiator is a trihaloalkyl compound, and the (C) addition-polymerizable ethylenically unsaturated bond-containing compound containing a group that can be oxidized by light is added. The photosensitive lithographic printing plate material according to claim 1, wherein: 7. The photosensitive lithographic printing plate material according to claim 1, wherein the aluminum support is anodized and then subjected to polyvinylphosphonic acid treatment. An alkaline developer having a pH of 10.0 to 12.5 after image exposure of the photosensitive lithographic printing plate material according to any one of claims 1 to 7 with a laser beam having an emission wavelength in a wavelength range of 350 nm to 450 nm. A process for making a photosensitive lithographic printing plate material, characterized in that: