JP2012189809A - Developing device for lithographic printing plate and developing method for lithographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a developing device for a lithographic printing plate precursor and a developing method for a lithographic printing plate precursor, able to stably produce a high quality lithographic printing plate.SOLUTION: The developing device for a lithographic printing plate precursor, which carries out development by conveying the lithographic printing plate precursor having a support and an image recording layer supported on the support and exposed. This developing device comprises: a first developing part having a first tank and configured to develop the image recording layer by impregnating the conveyed lithographic printing plate precursor with a developing liquid stored in the first tank; a second developing part disposed downstream of the first developing part in the direction of conveyance of the lithographic printing plate precursor and having a second tank storing a developing liquid; a replenishing part for replenishing the second tank with a fresh developing liquid; and a liquid feeder for feeding the developing liquid stored in the second tank to the first tank. The feeder feeds the developing liquid stored in the second tank to the first tank.

Description

  The present invention relates to a lithographic printing plate developing apparatus and a lithographic printing plate developing method.

A lithographic printing plate is produced using a lithographic printing plate precursor (PS plate) comprising a hydrophilic support and an oleophilic photosensitive resin layer (image recording layer) formed on the support.
As a method for producing a lithographic printing plate, the lithographic printing plate precursor is exposed using an original image such as a lithographic film, or directly exposed imagewise by laser light scanning with digital data, and then the image recording layer The lithographic printing plate precursor exposed with is developed with a developing device.

  Such a developing device, for example, leaves a portion to be an image portion of the image recording layer, and dissolves and removes the other unnecessary image recording layer with an alkaline developer having a pH of 10 or more to expose the support surface. To form a non-image portion. And a lithographic printing plate is produced by coat | covering a support body and the remaining image part with the gum liquid which mainly has hydrophilic resin.

  As described above, in the plate making process of a conventional lithographic printing plate precursor, a step of dissolving and removing an unnecessary image recording layer with a developer or the like is necessary after exposure, but it is closer to the neutral range in terms of environment and safety. It is important to enable processing with a developer and to reduce waste liquid, and in recent years, the demand has become stronger. For this reason, it is now desired to reduce the alkali of the developer.

  However, the reduction in alkali level of the developer gives a large load to the development process. For example, it is more difficult to remove the image recording layer than when a low alkaline developer or a normal alkaline developer is used, and when the developer becomes fatigued, the developing ability decreases, and the lithographic printing plate The image recording layer component may remain on the top.

  Here, as a configuration of the developing unit of the developing device, mainly the lithographic printing plate is transported horizontally without being immersed in the developer, and transported while being immersed in the developer stored in the tank. There is an immersion type.

  In the horizontal conveyance type, a developer is supplied to the conveyed lithographic printing plate using a spray. However, in this horizontal conveyance type configuration, there is a problem that the liquid is easily scattered by the liquid splash, and the scattered liquid dries and becomes crushed. Further, in the horizontal conveyance type configuration, the processing liquid is easily dried when not in operation, and the rubbing material (brush), the roller, and the like are also likely to be contaminated and debris due to drying. For this reason, a developing device employing an immersion method is used. However, even with this method, it is difficult to sufficiently dissolve the image recording layer with a low alkaline or non-alkaline developer. Further, when the developer is fatigued, the residue often floats in the developer stored in the tank.

  In view of this, there has been considered a method in which a plurality of developing units are provided in the transporting direction of the lithographic printing plate, and development is performed separately by the plurality of developing units (see, for example, Patent Document 1). According to this method, the image recording layer can be easily dissolved even with a low alkaline or non-alkaline developer.

JP 2007-52279 A

  By the way, as shown in Patent Document 1, in the immersion type developing device, it is necessary to appropriately replenish the developer in a tank storing the developer in order to maintain the developer in a state where the image recording layer can be normally developed. There is. In the configuration in which the developer is supplied to the upstream tank by overflowing the developer from the tank located downstream in the transport direction to the tank located immediately upstream, the amount of the developer supplied can be accurately controlled. It was impossible. For this reason, the state of the developer cannot be maintained, and a lithographic printing plate cannot be stably produced with high quality.

  The present invention has been made in view of the above circumstances, and provides a lithographic printing plate precursor developing apparatus and a lithographic printing plate precursor developing method capable of stably producing a high-quality lithographic printing plate. Objective.

(1) A lithographic printing plate precursor developing device for carrying out development by transporting a lithographic printing plate precursor having a support and an exposed image recording layer supported on the support,
A first developing section which has a first tank and develops the image recording layer by immersing the transported lithographic printing plate precursor in a developer stored in the first tank;
A second developing section, which is disposed downstream of the first developing section in the transport direction of the lithographic printing plate precursor and has a second tank for storing a developer;
A replenisher for replenishing the second tank with fresh developer;
A liquid feeding device for feeding the developer stored in the second tank from the second tank to the first tank, and
The liquid feeding device is a lithographic printing plate precursor developing device that feeds the developer stored in the second tank to the first tank.
(2) A method for developing a lithographic printing plate precursor using a developing device that transports and develops a lithographic printing plate precursor having a support and an exposed image recording layer supported on the support. ,
The developing device has a first tank, a first developing unit that develops the image recording layer by immersing the transported lithographic printing plate precursor in a developer stored in the first tank;
A second developing unit that is disposed downstream of the first developing unit in the transport direction of the lithographic printing plate precursor and has a second tank for storing a developer, and
Developing the image recording layer by immersing the planographic printing plate in a developer stored in the first tank;
Replenishing the developer to a second tank disposed downstream of the first tank in the transport direction of the planographic printing plate;
And a step of feeding the developer stored in the second tank to the first tank using a liquid feeding device.

  According to the present invention, it is possible to provide a lithographic printing plate precursor developing apparatus and a lithographic printing plate precursor developing method capable of stably producing a high-quality lithographic printing plate.

It is the schematic which shows the structure of the image development apparatus of the lithographic printing plate precursor of this invention. It is the schematic which shows the other structural example of the developing apparatus of the lithographic printing plate precursor of this invention.

  First, a planographic printing plate precursor that can be preferably used in the present invention will be described.

[Lithographic printing plate precursor]
The lithographic printing plate precursor that can be preferably used in the present invention comprises an image containing (A) a polymerization initiator, (B) a polymerizable compound, (C) a sensitizing dye, and (D) a binder polymer on a hydrophilic support. It has a recording layer, and more preferably, it has a protective layer on the image recording layer.

(A) Polymerization initiator The image recording layer preferably contains a polymerization initiator (hereinafter also referred to as an initiator compound). In the present invention, a radical polymerization initiator is preferably used.

  As the initiator compound, those known to those skilled in the art can be used without limitation, and specifically include, for example, trihalomethyl compounds, carbonyl compounds, organic peroxides, azo compounds, azide compounds, metallocene compounds, hexaarylbiphenyls. Examples include imidazole compounds, organic boron compounds, disulfone compounds, oxime ester compounds, onium salt compounds, and iron arene complexes. Among these, at least one selected from the group consisting of a hexaarylbiimidazole compound, an onium salt compound, a trihalomethyl compound, and a metallocene compound is preferable, and a hexaarylbiimidazole compound is particularly preferable. Two or more polymerization initiators may be used in combination as appropriate.

Examples of the hexaarylbiimidazole compound include lophine dimers described in European Patent 24,629, European Patent 10,7792, and US Pat. No. 4,410,621, such as 2,2′-bis (o-chlorophenyl) -4. , 4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-bromophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o , P-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetra (m-methoxyphenyl) Biimidazole, 2,2'-bis (o, o'-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-nitrophenyl) -4 4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-methylphenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o- Trifluoromethylphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and the like.
The hexaarylbiimidazole compound is particularly preferably used in combination with a sensitizing dye having a maximum absorption in the wavelength region of 300 to 450 nm.

  As the onium salt compound, a sulfonium salt, an iodonium salt, or a diazonium salt is preferably used. In particular, diaryliodonium salts and triarylsulfonium salts are preferably used.

  The onium salt compound is particularly preferably used in combination with an infrared absorber having a maximum absorption in a wavelength range of 750 to 1400 nm.

  As other polymerization initiators, polymerization initiators described in paragraph numbers [0071] to [0129] of JP-A-2007-206217 can be preferably used.

The polymerization initiator is preferably used alone or in combination of two or more.
The content of the polymerization initiator in the image recording layer is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and still more preferably 1.0% by mass with respect to the total solid content of the image recording layer. % To 10% by mass.

(B) Polymerizable compound The image recording layer preferably contains a polymerizable compound. The polymerizable compound is preferably an addition polymerizable compound having at least one ethylenically unsaturated double bond, more preferably a compound having at least one terminal ethylenically unsaturated bond, more preferably two or more. Chosen from. These have chemical forms such as monomers, prepolymers, ie dimers, trimers and oligomers, or mixtures thereof. Examples of monomers include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters and amides thereof, preferably unsaturated carboxylic acids. Esters of an acid and a polyhydric alcohol compound and amides of an unsaturated carboxylic acid and a polyamine compound are used. Further, addition reaction products of unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group and the like with monofunctional or polyfunctional isocyanates or epoxy, and monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. In addition, an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group and an addition reaction product of a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group, A substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, a compound group in which the unsaturated carboxylic acid is replaced with unsaturated phosphonic acid, styrene, vinyl ether or the like can be used. These are disclosed in JP-T-2006-508380, JP-A-2002-287344, JP-A-2008-256850, JP-A-2001-342222, JP-A-9-179296, JP-A-9-179297. JP-A-9-179298, JP-A-2004-294935, JP-A-2006-243493, JP-A-2002-275129, JP-A-2003-64130, JP-A-2003-280187, It is described in Japanese Laid-Open Patent Publication No. 10-333321.

  Specific examples of esters of unsaturated carboxylic acids and polyhydric alcohol compounds include acrylic acid esters such as ethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, Examples include methylolpropane triacrylate, hexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol tetraacrylate, sorbitol triacrylate, isocyanuric acid ethylene oxide (EO) -modified triacrylate, and polyester acrylate oligomer. Methacrylic acid esters include tetramethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, pentaerythritol trimethacrylate, bis [p- (3-methacryloxy-2-hydroxypropoxy) phenyl ] Dimethylmethane, bis- [p- (methacryloxyethoxy) phenyl] dimethylmethane, and the like.

  Specific examples of amide monomers of unsaturated carboxylic acids and polyvalent amine compounds include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis-methacrylic. Examples include amide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, and xylylene bismethacrylamide.

  Further, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable. Specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinylurethane compound containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (A) to a polyisocyanate compound having two or more isocyanate groups Etc.

^{_{CH 2 = C (R 4)}} COOCH 2 CH (R 5) OH (A)
(However, R ⁴ and R ⁵ represent H or CH _3. )

  Also, urethanes described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-A-2003-344997, and JP-A-2006-65210. Acrylates, JP-B 58-49860, JP-B 56-17654, JP-B 62-39417, JP-B 62-39418, JP-A 2000-250211, JP-A 2007-94138 Urethane compounds having an ethylene oxide-based skeleton described in the publication, US Pat. No. 7,153,632, JP-T 8-505958, JP-A 2007-293221, and JP-A 2007-293223. Urethane compounds having a hydrophilic group are also suitable.

  Also, photo-oxidizable polymerizable compounds described in JP-T-2007-506125 are suitable, and polymerizable compounds containing at least one urea group and / or tertiary amino group are particularly preferred. Specific examples include the following compounds.

  Details of the method of use, such as the structure of the polymerizable compound, whether it is used alone or in combination, and the amount added, can be arbitrarily set according to the performance design of the final lithographic printing plate precursor. The polymerizable compound is preferably used in the range of 5 to 75% by mass, more preferably 25 to 70% by mass, and particularly preferably 30 to 60% by mass with respect to the total solid content of the image recording layer.

  Among the polymerizable compounds, a polymerizable compound having a urethane bond or a urea bond in the molecule that has a high interaction property with the zwitterionic surfactant contained in the developer according to the present invention is effective for the effect of the present invention. It is particularly preferable in terms of expression.

(C) Sensitizing dye The image recording layer contains a sensitizing dye. The sensitizing dye is not particularly limited as long as it absorbs light at the time of image exposure to be in an excited state, supplies energy to the polymerization initiator by electron transfer, energy transfer or heat generation, and improves the polymerization start function. Can be used. In particular, a sensitizing dye having a maximum absorption in a wavelength range of 300 to 450 nm or 750 to 1400 nm is preferably used.

  Examples of the sensitizing dye having maximum absorption in the wavelength range of 300 to 450 nm include merocyanines, benzopyrans, coumarins, aromatic ketones, anthracenes, styryls, oxazoles and the like.

  Of the sensitizing dyes having an absorption maximum in the wavelength range of 300 to 450 nm, a dye more preferable from the viewpoint of high sensitivity is a dye represented by the following general formula (IX).

In General Formula (IX), A represents an aryl group or a heteroaryl group which may have a substituent, and X represents an oxygen atom, a sulfur atom, or ═N (R ₃ ). R ₁ , R ₂ and R ₃ each independently represent a monovalent nonmetallic atomic group, and A and R ₁ or R ₂ and R ₃ are bonded to each other to form an aliphatic or aromatic ring May be formed.

General formula (IX) will be described in more detail. R ₁ , R ₂ and R ₃ are each independently a monovalent nonmetallic atomic group, preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, substituted or unsubstituted An aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, a hydroxyl group, and a halogen atom.

As the aryl group or heteroaryl group which may have a substituent represented by A in general formula (IX), a substituted or unsubstituted aryl group, a substituted or an unsubstituted group described by R ₁ , R ₂ and R ₃ , respectively. The thing similar to an unsubstituted heteroaryl group is mentioned.

  Specific examples of such a sensitizing dye include paragraph numbers [0047] to [0053] of JP-A No. 2007-58170, paragraph numbers [0036] to [0037] of JP-A No. 2007-93866, and JP-A No. 2007-72816. The compounds described in paragraph Nos. [0042] to [0047] are preferably used.

  JP-A-2006-189604, JP-A-2007-171406, JP-A-2007-206216, JP-A-2007-206217, JP-A-2007-225701, JP-A-2007-225702, JP-A-2007-316582 Sensitizing dyes described in JP-A-2007-328243 can also be preferably used.

  Next, a sensitizing dye having a maximum absorption in the wavelength region of 750 to 1400 nm (hereinafter sometimes referred to as “infrared absorber”) will be described. As the infrared absorber, a dye or a pigment is preferably used.

  As the dye, commercially available dyes and known dyes described in documents such as “Dye Handbook” (edited by the Society for Synthetic Organic Chemistry, published in 1970) can be used. Specifically, dyes such as azo dyes, metal complex azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, metal thiolate complexes Is mentioned. Particularly preferred among these dyes are cyanine dyes, squarylium dyes, pyrylium salts, nickel thiolate complexes, and indolenine cyanine dyes. Further, cyanine dyes and indolenine cyanine dyes are preferred, and particularly preferred examples include cyanine dyes represented by the following general formula (a).

In the general formula (a), ^{X 1} represents a hydrogen atom, a halogen atom, -NPh2, a group shown -X2-L1 or less. Here, X2 represents an oxygen atom, a nitrogen atom or a sulfur atom, L1 represents a hydrocarbon group having 1 to 12 carbon atoms, an aryl group having a hetero atom (N, S, O, halogen atom, Se), hetero The C1-C12 hydrocarbon group containing an atom is represented. Xa- has the same meaning as Za- described later, and Ra represents a substituent selected from a hydrogen atom, an alkyl group, an aryl group, a substituted or unsubstituted amino group, and a halogen atom.

R ¹ and R ² each independently represent a hydrocarbon group having 1 to 12 carbon atoms. In view of storage stability of the image recording layer coating solution, R ¹ and R ² are preferably hydrocarbon groups having 2 or more carbon atoms. R ¹ and R ² may be connected to each other to form a ring, and when a ring is formed, it is particularly preferable to form a 5-membered ring or a 6-membered ring.

Ar ¹ and Ar ² may be the same or different and each represents an aryl group which may have a substituent. Preferred aryl groups include a benzene ring and a naphthalene ring. Moreover, as a preferable substituent, a C12 or less hydrocarbon group, a halogen atom, and a C12 or less alkoxy group are mentioned. Y ¹ and Y ² may be the same or different and each represents a sulfur atom or a dialkylmethylene group having 12 or less carbon atoms. R ³ and R ⁴ may be the same or different and each represents a hydrocarbon group having 20 or less carbon atoms which may have a substituent. Preferred substituents include alkoxy groups having 12 or less carbon atoms, carboxyl groups, and sulfo groups. R ⁵ , R ⁶ , R ⁷ and R ⁸ may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 12 or less carbon atoms. From the availability of raw materials, a hydrogen atom is preferred.

  Za- represents a counter anion. However, Za- is not necessary when the cyanine dye represented by formula (a) has an anionic substituent in its structure and neutralization of charge is not necessary. Preferred Za- is a halogen ion, a perchlorate ion, a tetrafluoroborate ion, a hexafluorophosphate ion, and a sulfonate ion, particularly preferably a perchlorate ion, a hexagonal acid, from the viewpoint of storage stability of the image recording layer coating solution. Fluorophosphate ions and aryl sulfonate ions.

  Specific examples of the cyanine dye represented by formula (a) that can be suitably used include paragraph numbers [0017] to [0019] of JP-A No. 2001-133969, and paragraph numbers of JP-A No. 2002-023360 [0016]. ] To [0021], compounds described in paragraphs [0012] to [0037] of JP-A No. 2002-040638, preferably paragraphs [0034] to [0041] of JP-A No. 2002-278057, JP-A 2008- The compounds described in paragraph Nos. [0080] to [0086] of No. 195018, particularly preferably the compounds described in paragraph Nos. [0035] to [0043] of JP-A-2007-90850 are exemplified.

  In addition, compounds described in paragraph numbers [0008] to [0009] of JP-A No. 5-5005 and paragraph numbers [0022] to [0025] of JP-A No. 2001-222101 can also be preferably used.

  Only 1 type may be used for an infrared absorption dye, and it may use 2 or more types together, and may use infrared absorbers other than infrared absorption dyes, such as a pigment, together. As the pigment, compounds described in paragraph numbers [0072] to [0076] of JP-A-2008-195018 are preferable.

  The preferred content of the sensitizing dye is preferably 0.05 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, and particularly preferably 0.2 to 100 parts by mass with respect to 100 parts by mass of the total solid content of the image recording layer. 10 parts by mass.

(D) Binder polymer The image recording layer contains a binder polymer. As the binder polymer, a polymer that can carry the image recording layer component on the support and can be removed by a developer is used. As the binder polymer, (meth) acrylic polymer, polyurethane, polyvinyl alcohol, polyvinyl butyral, polyvinyl formal, polyamide, polyester, epoxy and the like are used. In particular, (meth) acrylic polymers, polyurethane, and polyvinyl butyral are preferably used.

  In the present invention, “(meth) acrylic polymer” means (meth) acrylic acid, (meth) acrylic acid ester (alkyl ester, aryl ester, allyl ester, etc.), (meth) acrylamide, and (meth). A copolymer having a (meth) acrylic acid derivative such as an acrylamide derivative as a polymerization component. “Polyurethane” refers to a polymer produced by a condensation reaction of a compound having two or more isocyanate groups and a compound having two or more hydroxyl groups. “Polyvinyl butyral” refers to a polymer synthesized by reacting polyvinyl alcohol obtained by saponifying part or all of polyvinyl acetate and butyraldehyde under an acidic condition (acetalization reaction). The polymer which introduce | transduced the acid group etc. by the method etc. by making the compound which has the hydroxyl group and acid group etc. which were made react is also contained.

A preferred example of the (meth) acrylic polymer in the present invention includes a polymer having a repeating unit having an acid group. Examples of the acid group include a carboxylic acid group, a sulfonic acid group, a phosphonic acid group, a phosphoric acid group, and a sulfonamide group, and a carboxylic acid group is particularly preferable.
As the repeating unit having an acid group, a repeating unit derived from (meth) acrylic acid or one represented by the following general formula (I) is preferably used.

In general formula (I), R ¹ represents a hydrogen atom or a methyl group, and R ² represents a single bond or an n + 1 valent linking group. A represents an oxygen atom or —NR ³ —, and R ³ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. n represents an integer of 1 to 5.

The linking group represented by R ² in the general formula (I) is composed of one or more atoms selected from the group consisting of a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom and a halogen atom. The number of atoms constituting the linking group represented by R ² is preferably 1-80. Specifically, an alkylene group, a substituted alkylene group, an arylene group, a substituted arylene group, and the like can be mentioned. These divalent groups are linked in multiples by any of an amide bond, an ether bond, a urethane bond, a urea bond, and an ester bond. You may have the structure made. As R ² , a single bond, an alkylene group, a substituted alkylene group, or at least one of an alkylene group and a substituted alkylene group is linked by at least one of an amide bond, an ether bond, a urethane bond, a urea bond, and an ester bond. Preferably, the structure is a single bond, an alkylene group having 1 to 5 carbon atoms, a substituted alkylene group having 1 to 5 carbon atoms, or an alkylene group having 1 to 5 carbon atoms and a substituted alkylene group having 1 to 5 carbon atoms. A structure in which at least one of an amide bond, an ether bond, a urethane bond, a urea bond, and an ester bond is connected to each other is particularly preferable, and is a single bond, an alkylene group having 1 to 3 carbon atoms, or an alkyl group having 1 to 3 carbon atoms. Substituted alkylene groups, or alkylene groups having 1 to 3 carbon atoms and substituted alkylene groups having 1 to 3 carbon atoms Most preferably, at least one of these has a structure in which a plurality of at least one of amide bond, ether bond, urethane bond, urea bond and ester bond are linked.

  Examples of the substituent in the substituted alkylene group and the substituted arylene group include a monovalent non-metallic atomic group excluding a hydrogen atom, a halogen atom (—F, —Br, —Cl, —I), a hydroxyl group, Cyano group, alkoxy group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkylcarbonyl group, arylcarbonyl group, acyl group, carboxyl group and its conjugate base group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, aryl Group, alkenyl group, alkynyl group and the like.

R ³ is preferably a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, particularly preferably a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, and most preferably a hydrogen atom or a methyl group. n is preferably 1 to 3, particularly preferably 1 or 2, and most preferably 1.

The ratio (mol%) of the repeating unit having an acid group in all repeating units of the (meth) acrylic polymer is preferably 1 to 70% from the viewpoint of developability. Considering compatibility between developability and printing durability, 1 to 50% is more preferable, and 1 to 30% is particularly preferable.
The acid value of the (meth) acrylic polymer is preferably 10 to 250 mg-KOH / g.

  The (meth) acrylic polymer used in the present invention preferably further has a crosslinkable group. Here, the crosslinkable group is a group that crosslinks the polymer in the course of radical polymerization reaction that occurs in the image recording layer when the lithographic printing plate precursor is exposed. Although it will not specifically limit if it is a group of such a function, For example, an ethylenically unsaturated bond group, an amino group, an epoxy group etc. are mentioned as a functional group which can be addition-polymerized. Moreover, the functional group which can become a radical by light irradiation may be sufficient, and as such a crosslinkable group, a thiol group, a halogen group, etc. are mentioned, for example. Of these, an ethylenically unsaturated bond group is preferable. As the ethylenically unsaturated bond group, a styryl group, a (meth) acryloyl group, and an allyl group are preferable.

  For example, free radicals (polymerization initiation radicals or growth radicals in the polymerization process of a polymerizable compound) are added to the crosslinkable functional group of the polymer, and the polymer is added directly between polymers or via a polymerization chain of the polymerizable compound. As a result of the polymerization, crosslinks are formed between the polymer molecules and cured. Alternatively, atoms in the polymer (for example, hydrogen atoms on carbon atoms adjacent to the functional bridging group) are extracted by free radicals to form polymer radicals that are bonded to each other, thereby interpolymer molecules Crosslinks are formed and cured.

  The content of the crosslinkable group in the (meth) acrylic polymer (content of unsaturated double bond capable of radical polymerization by iodine titration) is preferably 0.01 to 10.0 mmol per 1 g of the polymer. Preferably it is 0.05-9.0 mmol, Most preferably, it is 0.1-8.0 mmol.

  The (meth) acrylic polymer used in the present invention includes, in addition to the repeating unit having an acid group and the repeating unit having a crosslinkable group, a repeating unit corresponding to an alkyl (meth) acrylate or an aralkyl ester, ) It may have a repeating unit corresponding to acrylamide or a derivative thereof, a repeating unit corresponding to α-hydroxymethyl acrylate, or a repeating unit corresponding to a styrene derivative. The alkyl group of the (meth) acrylic acid alkyl ester is preferably an alkyl group having 1 to 5 carbon atoms and an alkyl group having the aforementioned substituent having 2 to 8 carbon atoms, and a methyl group is more preferable. Examples of the (meth) acrylic acid aralkyl ester include benzyl (meth) acrylate. Examples of (meth) acrylamide derivatives include N-isopropylacrylamide, N-phenylmethacrylamide, N- (4-methoxycarbonylphenyl) methacrylamide, N, N-dimethylacrylamide, morpholinoacrylamide and the like. Examples of the α-hydroxymethyl acrylate include ethyl α-hydroxymethyl acrylate and cyclohexyl α-hydroxymethyl acrylate. Examples of styrene derivatives include styrene and 4-tertbutylstyrene.

As a suitable example of the polyurethane in the present invention, paragraph numbers [00099] to [0210] of JP-A No. 2007-187836, paragraph numbers [0019] to [0100] of JP-A No. 2008-276155, JP-A No. 2005-250438. Examples include polyurethanes described in paragraph numbers [0018] to [0107] of JP, No. 2005-250158, and paragraphs [0021] to [0083] of JP-A-2005-250158.
As a suitable example of the polyvinyl butyral in this invention, the polyvinyl butyral of Paragraph Nos. [0006]-[0013] of Unexamined-Japanese-Patent No. 2001-75279 can be mentioned.

Similarly to the (meth) acrylic polymer, polyurethane and polyvinyl butyral preferably have an acid group such as a carboxylic acid group, and more preferably have a crosslinkable group such as an ethylenically unsaturated group. The preferred ranges of the acid value and the crosslinkable group content are the same as those of the (meth) acrylic copolymer.
A polyurethane having a urethane bond having a high interaction property with the zwitterionic surfactant contained in the developer according to the present invention is particularly preferable for effectively expressing the effects of the present invention.

A part of the acid groups in the binder polymer may be neutralized with a basic compound. Examples of basic compounds include compounds containing basic nitrogen, alkali metal hydroxides, and quaternary ammonium salts of alkali metals.
The binder polymer preferably has a mass average molecular weight of 5,000 or more, more preferably 10,000 to 300,000, and a number average molecular weight of 1,000 or more, preferably 2000 to 250,000. More preferred. The polydispersity (mass average molecular weight / number average molecular weight) is preferably 1.1 to 10.
A binder polymer may be used independently or may be used in mixture of 2 or more types. The content of the binder polymer is preferably 5 to 75% by mass, more preferably 10 to 70% by mass with respect to the total solid content of the image recording layer, from the viewpoint of good image area strength and image formability. More preferably, it is -60 mass%.
The total content of the polymerizable compound and the binder polymer is preferably 90% by mass or less with respect to the total solid content of the image recording layer. If it exceeds 90% by mass, the sensitivity and developability may be lowered. More preferably, it is 35-80 mass%.

  In general, the larger the ratio of the polymerizable compound to the binder polymer in the image recording layer of the lithographic printing plate precursor, the better the permeability of the developer into the image recording layer and the better the developability. The mass ratio of the polymerizable compound / binder polymer in the image recording layer of the lithographic printing plate precursor according to the invention is preferably 1.2 or more, more preferably 1.25 to 4.5, and particularly preferably 2 to 4. .

  The image recording layer preferably contains a chain transfer agent. The chain transfer agent is defined, for example, in Polymer Dictionary 3rd Edition (edited by Polymer Society, 2005) pages 683-684. As the chain transfer agent, for example, a compound group having SH, PH, SiH, GeH in the molecule is used. These can generate a radical by donating hydrogen to a radical species having low activity, or can be oxidized and then deprotonated to generate a radical. In the image recording layer of the present invention, in particular, thiol compounds (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzthiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles, etc.) Can be preferably used. Preferable examples include thiol compounds described in paragraph numbers [0097] to [0109] of JP-A-2007-58170.

  The content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 1 to 10 parts by mass, and particularly preferably 1 to 5 parts by mass with respect to 100 parts by mass of the total solid content of the image recording layer. .

(Other image recording layer components)
The image recording layer can further contain various additives as required. Additives include surfactants for improving developability and improving the surface of the coating, microcapsules for achieving both developability and printing durability, and improving the developability and dispersion stability of microcapsules. Hydrophilic polymer, colorant and print-out agent for visually recognizing image area and non-image area, polymerization inhibitor for preventing unnecessary thermal polymerization of radical polymerizable compound during production or storage of image recording layer Hydrophobic low molecular weight compounds such as higher fat derivatives to prevent polymerization inhibition by oxygen, inorganic fine particles and organic fine particles for improving the cured film strength of the image area, hydrophilic low molecular weight compounds for improving developability, sensitivity Examples thereof include a co-sensitizer for improvement and a plasticizer for improvement of plasticity. These additives are all known, for example, paragraph numbers [0161] to [0215] of JP-A-2007-206217, paragraph number [0067] of JP-T-2005-509192, and JP-A-2004-310000. The compounds described in paragraphs [0023] to [0026] and [0059] to [0066] can be used. As for the surfactant, a surfactant which may be added to the developer described later can also be used.

<Formation of image recording layer>
The image recording layer is formed by preparing or applying a coating solution by dispersing or dissolving the necessary components described above in a solvent. Examples of the solvent used include methyl ethyl ketone, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-methoxyethyl acetate, 1-methoxy-2-propyl acetate, and γ-butyllactone. It is not limited. A solvent is used individually or in mixture. The solid content concentration of the coating solution is preferably 1 to 50% by mass.

The coating amount (solid content) of the image recording layer obtained after coating and drying is preferably 0.3 to 3.0 g / m ² . Various methods can be used as a coating method. Examples thereof include bar coater coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating, and roll coating.

<Protective layer>
The lithographic printing plate precursor used in the production method of the present invention is provided with a protective layer (oxygen blocking layer) on the image recording layer in order to block the diffusion and penetration of oxygen that hinders the polymerization reaction during exposure. As a material for the protective layer, either a water-soluble polymer or a water-insoluble polymer can be appropriately selected and used, and two or more kinds can be mixed and used as necessary. Specific examples include polyvinyl alcohol, modified polyvinyl alcohol, polyvinyl pyrrolidone, water-soluble cellulose derivatives, poly (meth) acrylonitrile, and the like. Among these, it is preferable to use a water-soluble polymer having relatively excellent crystallinity, and specifically, polyvinyl alcohol as the main component is most excellent in basic characteristics such as oxygen barrier properties and development removability. Give a good result.

  The polyvinyl alcohol used for the protective layer may be partially substituted with an ester, an ether or an acetal as long as it contains an unsubstituted vinyl alcohol unit for having necessary oxygen barrier properties and water solubility. Similarly, some of them may have other copolymer components. Polyvinyl alcohol can be obtained by hydrolyzing polyvinyl acetate. Specific examples of polyvinyl alcohol include those having a hydrolysis degree of 69.0 to 100 mol% and a number of repeating units of 300 to 2400. Can do. Specifically, PVA-102, PVA-103, PVA-105, PVA-110, PVA-117, PVA-117H, PVA-120, PVA-124, PVA-124H, PVA-CS, manufactured by Kuraray Co., Ltd. PVA-CST, PVA-HC, PVA-203, PVA-204, PVA-205, PVA-210, PVA-217, PVA-220, PVA-224, PVA-235, PVA-217EE, PVA-217E, PVA- 220E, PVA-224E, PVA-403, PVA-405, PVA-420, PVA-424H, PVA-505, PVA-617, PVA-613, PVA-706, L-8 and the like. These can be used alone or in combination. The content rate in the protective layer of polyvinyl alcohol becomes like this. Preferably it is 20-95 mass%, More preferably, it is 30-90 mass%.

  Moreover, well-known modified polyvinyl alcohol can also be used preferably. In particular, acid-modified polyvinyl alcohol having a carboxylic acid group or a sulfonic acid group is preferably used. Specific examples include polyvinyl alcohols described in JP-A-2005-250216 and JP-A-2006-259137.

  In the case of using a mixture of polyvinyl alcohol and another material, as a component to be mixed, modified polyvinyl alcohol, polyvinyl pyrrolidone or a modified product thereof is preferable from the viewpoint of oxygen barrier properties, development removability, and the content in the protective layer is It is 3.5-80 mass%, Preferably it is 10-60 mass%, More preferably, it is 15-30 mass%.

  As another composition of the protective layer, glycerin, dipropylene glycol and the like can be added in an amount corresponding to several mass% with respect to the polymer to impart flexibility. In addition, anionic surfactants such as sodium alkyl sulfate and sodium alkyl sulfonate, amphoteric surfactants such as alkylaminocarboxylate and alkylaminodicarboxylate, and nonionic surfactants such as polyoxyethylene alkylphenyl ether are polymerized. It is possible to add several mass% with respect to.

  Further, the protective layer preferably contains an inorganic layered compound for the purpose of improving oxygen barrier properties and image recording layer surface protection. Among inorganic layered compounds, fluorine-based swellable synthetic mica, which is a synthetic inorganic layered compound, is particularly useful. Specifically, inorganic layered compounds described in JP-A No. 2005-119273 are preferable.

The coating amount of the protective layer is a coating amount after drying is preferably 0.05 to 10 g / ^{m 2,} when the protective layer contains the inorganic stratiform compound, more preferably 0.1-5 g / ^{m 2,} the inorganic When not containing a layered compound, 0.5-5 g / m < ² > is still more preferable.

<Support>
The support used for the lithographic printing plate precursor is not particularly limited as long as it is a dimensionally stable plate-like hydrophilic support. In particular, an aluminum plate is preferable. Prior to using the aluminum plate, it is preferable to perform a surface treatment such as roughening treatment or anodizing treatment. The surface roughening treatment of the aluminum plate is performed by various methods. For example, mechanical surface roughening treatment, electrochemical surface roughening treatment (surface roughening treatment for dissolving the surface electrochemically), chemical treatment, etc. Surface roughening treatment (roughening treatment that chemically selectively dissolves the surface). For these treatments, the methods described in JP-A 2007-206217, paragraphs [0241] to [0245] can be preferably used.

The support preferably has a center line average roughness of 0.10 to 1.2 μm. Within this range, good adhesion to the image recording layer, good printing durability and good stain resistance can be obtained.
The color density of the support is preferably 0.15 to 0.65 as a reflection density value. Within this range, good image formability by preventing halation during image exposure and good plate inspection after development can be obtained.
The thickness of the support is preferably from 0.1 to 0.6 mm, more preferably from 0.15 to 0.4 mm, still more preferably from 0.2 to 0.3 mm.

(Support hydrophilic treatment, undercoat layer)
In the planographic printing plate precursor, in order to improve the hydrophilicity of the non-image area and prevent printing stains, the support surface may be subjected to a hydrophilic treatment or an undercoat layer may be provided between the support and the image recording layer. Is preferred.

  Examples of the hydrophilization treatment of the support surface include an alkali metal silicate treatment method in which the support is immersed or electrolyzed in an aqueous solution such as sodium silicate, a treatment method with potassium fluoride zirconate, a treatment method with polyvinylphosphonic acid, etc. The method of immersing in an aqueous polyvinylphosphonic acid solution is preferably used.

As the undercoat layer, an undercoat layer having a compound having an acid group such as phosphonic acid, phosphoric acid or sulfonic acid is preferably used. These compounds preferably further contain a polymerizable group in order to improve adhesion to the image recording layer. As the polymerizable group, an ethylenically unsaturated bond group is preferable. Furthermore, compounds having a hydrophilicity-imparting group such as an ethyleneoxy group can also be mentioned as suitable compounds.
These compounds may be low molecular compounds or high molecular polymers. These compounds may be used as a mixture of two or more if necessary.

  A silane coupling agent having an ethylenically unsaturated bond group capable of addition polymerization described in JP-A-10-282679 and a phosphorus compound having an ethylenically unsaturated bond group described in JP-A-2-304441 are suitable. It is mentioned in. A crosslinkable group (preferably an ethylenically unsaturated bond group) described in JP-A-2005-238816, JP-A-2005-125649, JP-A-2006-239867, and JP-A-2006-215263 is formed on the support surface. It is also preferable to contain a low molecular or high molecular compound having a functional group that interacts and a hydrophilic group.

The undercoat layer is applied by a known method. The coating amount (solid content) of the undercoat layer is preferably from ^{0.1~100mg / m 2, 1~30mg / m} 2 is more preferable.

<Back coat layer>
If necessary, a back coat can be provided on the back surface (surface opposite to the image recording layer) of the support. As the back coat, for example, a layer made of an organic polymer compound described in JP-A-5-45885, an organic metal compound or an inorganic metal compound described in JP-A-6-35174 is hydrolyzed and Preferred examples include a coating layer made of a metal oxide obtained by polycondensation. Among them, it is inexpensive to use a silicon alkoxy compound such as Si (OCH ₃ ) ₄ , Si (OC ₂ H ₅ ) ₄ , Si (OC ₃ H ₇ ) ₄ , Si (OC ₄ H ₉ ) _4. It is preferable in terms of easy availability.

Below, the preparation method of the lithographic printing plate which concerns on this invention is described.
[Preparation method of lithographic printing plate]
A lithographic printing plate is produced by subjecting the lithographic printing plate precursor according to the present invention to image exposure and development.

<Image exposure process>
The lithographic printing plate precursor is imagewise exposed by laser exposure through a transparent original image having a line image, a halftone dot image or the like, or by laser beam scanning by digital data.
The wavelength of the light source is preferably 300 to 450 nm or 750 to 1400 nm. In the case of 300 to 450 nm, a lithographic printing plate precursor having a sensitizing dye having an absorption maximum in this region in the image recording layer is used, and in the case of 750 to 1400 nm, infrared rays which are sensitizing dyes having absorption in this region. A lithographic printing plate precursor containing an absorbent is used. As the light source of 300 to 450 nm, a semiconductor laser is suitable. As a light source of 750 to 1400 nm, a solid laser and a semiconductor laser emitting infrared rays are suitable. The exposure mechanism may be any of an internal drum system, an external drum system, a flat bed system, and the like.

  Next, the configuration of the developing device of the present invention will be described with reference to the drawings.

  FIG. 1 is a diagram schematically showing the configuration of the developing device of the present invention.

  The developing device 1 develops the lithographic printing plate precursor 10 while producing the lithographic printing plate while carrying the lithographic printing plate precursor 10 that has been exposed to the image recording unit in advance along the conveyance path. .

  The developing device 1 includes a preheating unit 50, a first processing unit 2, a second processing unit 3, and a third processing unit 4 in order from the upstream side of the transported planographic printing plate precursor 10 in the transport direction. And a drying unit 52.

  The preheating unit 50 has a heating unit. The preheating unit 50 preheats the planographic printing plate precursor 10 with a heating unit prior to development processing. Preheating is performed at 100 ° C. for 10 seconds. The heating time and the heating temperature can be appropriately changed depending on the plate material. The heating time is preferably set to 5 to 30 seconds. Moreover, it is preferable to set heating temperature at 60-140 degreeC, More preferably, it is 80-120 degreeC. In addition, the preheating part does not necessarily need to be provided, and may be omitted without providing the preheating part according to the configuration of the lithographic printing plate precursor.

  The first processing unit 2 has a tank 20. The tank 20 stores a predetermined amount of the developer L1. The first processing unit 2 develops the exposed portion of the image recording layer by immersing the transported lithographic printing plate precursor 10 in the developer L1. In the configuration shown in FIG. 1, the first processing unit 2 functions as a first developing unit.

  The first processing unit 2 includes a conveyance roller pair 22 and a conveyance roller pair 24. The conveyance roller pair 22 is arranged on the upstream side of the conveyance path in the first processing unit 2 and carries the lithographic printing plate precursor 10 to be conveyed while being immersed in the developer L1 stored in the tank 20. The conveyance roller pair 24 is arranged on the downstream side of the conveyance path in the first processing unit 2, and carries out the lithographic printing plate precursor 10 from the first processing unit 2.

  The first processing unit 2 includes a rubbing member 26. The rubbing member 26 is disposed between the conveyance roller pair 22 and the conveyance roller pair 24 on the conveyance path in the first processing unit 2. The rubbing member 26 removes the non-exposed portion of the image recording layer by rubbing the image recording layer of the planographic printing plate precursor immersed in the developer L1 stored in the tank 20. Since the rubbing member 26 rubs the planographic printing plate precursor 10 while being immersed in the developer L1, the developer hardly scatters. Thereby, it is possible to avoid the occurrence of contamination and waste in the developing device due to the scattering of the developing solution.

  When the image recording layer has an overcoat layer, the overcoat layer is simultaneously removed by the rubbing member 26.

  The rubbing member may be anything as long as it can rub the image recording surface of the lithographic printing plate precursor. In particular, a rotating brush roll capable of rubbing the image recording layer by rotating around the rotation axis is used. It is preferable. As such a rotating brush roll, it is preferable to use, for example, a known channel brush, twisting brush, planting brush, carpet brush, and Morton roller.

  When rubbing in a state immersed in the treatment liquid using a rotating brush roll or the like, from the viewpoint of dispersion of the liquid, the rubbing member is preferably in a state where 1/3 or more of the diameter is immersed in the treatment liquid, More preferably, 2/3 or more, more preferably 3/4 or more is immersed.

  As the channel brush, long so-called channel brushes as disclosed in Japanese Utility Model Laid-Open Nos. 62-167253, 4-63447, 4-64128, and Japanese Patent Laid-Open No. 6-186751 are disclosed. A (band-like brush) that is spirally wound around the surface of the roller body is used. As the torsion brush, a torsion brush inserted into a spiral groove provided in the shaft as disclosed in JP-A-3-87832 and spirally wound around the shaft is used. As an implantation brush, what is created by the method of making a small hole in a shaft roller and implanting a brush material is used. As a carpet brush, an elongated belt in which a hair material is woven into a woven fabric is wound around the shaft roller as disclosed in JP 2001-5193 A and JP 2001-66788 A. Is used. As the Molton roller, a roller part disclosed in JP-A-10-198044 is covered with a cylindrical sliding contact material made of a fiber knitted fabric and the end on the mounting side is tightened. it can.

  When a rotating member is used as the rubbing member, the number of rotations of the rubbing member is preferably as fast as possible in order to improve the removability of the image recording layer of the non-exposed portion of the lithographic printing plate precursor, but the durability of the developing device From the viewpoints of properties, manufacturing costs, dispersion of the processing liquid, and damage to the exposed portion of the lithographic printing plate precursor, 30 to 1000 rpm, more preferably 50 to 500 rpm is preferable.

  When using a brush as a rubbing member, the number of the brush should just be one or more, and may have more than one. In the case of two or more, one or more may be rotated in the direction opposite to the processing direction of the planographic printing plate precursor. Further, when a rotating rubbing member is used, the developing process may be performed while the rubbing member is swung in the direction of the rotation axis. By swinging the rubbing member in the rotation axis direction, the non-image portion of the lithographic printing plate precursor can be removed more effectively, and a higher quality lithographic printing plate can be produced.

  As the material of the brush used for the rubbing member, natural fibers such as horse hair and pig hair, artificial fibers, metal fibers, and the like are known, but artificial fibers are preferable from the viewpoint of chemical resistance. Man-made fibers include polyamides such as nylon 6, nylon 6,6, nylon 6,10, nylon 6,12 and nylon 12, polyesters such as polyethylene terephthalate and polybutylene terephthalate (PBT), polyacrylonitrile, poly (meta ) Polyacrylics such as alkyl acrylate, polyolefins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride and polyvinylidene chloride, celluloses such as acetyl cellulose, polyurethanes such as polyurethane, polyphenylene sulfite, ethylene tetrafluoride Fluorine resins such as ethylene copolymers and polyvinylidene fluoride are used, but considering elasticity, rigidity, wear resistance, heat resistance, chemical resistance, water supply, moisture absorption, etc., nylon 6, nylon 6, 6, Nylon 6 · 10, Nai 6/12, nylon 12, polypropylene, polybutylene terephthalate, and polyethylene terephthalate are preferable, and nylon nylon 6.6, nylon 6.10, 6.12, nylon 12, polybutylene terephthalate (PBT), and polypropylene are more preferable. It is done. Of the polyesters, polybutylene terephthalate (PBT) is particularly preferable. Of the polyolefins, polypropylene is particularly preferred.

  The thickness of the brush hair is not particularly limited, but is preferably 0.01 mm to 1.0 mm, more preferably 0.1 mm to 0.5 mm. This is because if the thickness of the brush is thinner than 0.01 mm, the rubbing property is inferior, and if it is thicker than 1.0 mm, the plate surface is easily scratched. Further, the length of the brush bristles is not particularly limited, but is usually in the range of 3 mm to 50 mm. This is because if the length is shorter than 3 mm, the contact with the lithographic printing plate precursor becomes non-uniform and the plate surface is easily scratched. On the other hand, if the length is longer than 50 mm, no advantage in development processing can be found by increasing the length, which is disadvantageous economically. In the case of a Molton roller, since the cylindrical sliding contact material which consists of a knitted material is covered, regulation of the thickness and length of a hair material is unnecessary.

  The second processing unit 3 has a tank 30. The tank 30 stores a predetermined amount of the developer L2. In the configuration shown in FIG. 1, the second processing unit 3 functions as a second developing unit.

  The second processing unit 3 includes a transport roller pair 32 and a transport roller pair 34. The conveyance roller pair 32 is arranged on the upstream side of the conveyance path in the second processing unit 3, and carries the lithographic printing plate precursor 10 carried out from the first processing unit 2 into the second processing unit 3. The conveyance roller pair 34 is arranged on the downstream side of the conveyance path in the second processing unit 3, and carries the lithographic printing plate precursor 10 out of the second processing unit 3. The planographic printing plate precursor 10 is conveyed substantially horizontally between the conveyance roller pair 32 and the conveyance roller pair 34.

  Furthermore, the 2nd process part 3 has a pair of spray pipe | tube 31 arrange | positioned in parallel with each other. The pair of spray pipes 31 are arranged so as to sandwich the conveyance path between them. In addition, the pair of spray pipes 31 is disposed between the conveyance roller pair 32 and the conveyance roller pair 34 on the conveyance path in the second processing unit 3.

  The pair of spray tubes 31 sprays the developer L2 on the transported lithographic printing plate precursor 10. In this way, the second processing unit 3 supplementarily develops the exposed portion of the image recording layer that remains without being developed by the first processing unit 2, and flushes the residue adhering to the lithographic printing plate precursor 10. Is possible. The processing unit 3 includes a mechanism for feeding the developer L2 stored in the tank 30 to the spray pipe 31, and the developer L2 discharged from the spray pipe 31 returns to the tank 30 and is circulated.

  The third processing unit 4 has a tank 40. A predetermined amount of developer L3 is stored in the tank 40. In the configuration shown in FIG. 1, the third processing unit 4 functions as a developing unit in the same manner as the second processing unit 3.

  The third processing unit 4 includes a conveyance roller pair 42 and a conveyance roller pair 44. The conveyance roller pair 42 is arranged on the upstream side of the conveyance path in the third processing unit 4, and carries the lithographic printing plate precursor 10 carried out from the second processing unit 3 into the third processing unit 4. The conveyance roller pair 44 is arranged on the downstream side of the conveyance path in the third processing unit 4, and carries out the lithographic printing plate precursor 10 from the third processing unit 4. The planographic printing plate precursor 10 is transported substantially horizontally between the transport roller pair 42 and the transport roller pair 44.

  Furthermore, the 3rd process part 4 has a pair of spray pipe | tube 41 arrange | positioned in parallel with each other. The pair of spray pipes 41 are arranged so as to sandwich the conveyance path between them. In addition, the pair of spray pipes 41 is disposed between the conveyance roller pair 42 and the conveyance roller pair 44 on the conveyance path in the third processing unit 4.

  The pair of spray pipes 41 sprays the developer L3 onto the transported lithographic printing plate precursor 10 so that the first processing unit 2 and the exposure unit of the image recording layer that remains without being developed in the second processing unit 3 It is possible to wash away the residue adhering to the lithographic printing plate precursor 10. The third processing unit 4 includes a mechanism for feeding the developer L3 stored in the tank 40 to the spray pipe 41. The developer L3 discharged from the spray pipe 41 returns to the tank 40 and is circulated. .

  The drying unit 52 dries the lithographic printing plate precursor 10 carried out from the third processing unit 4. The drying temperature (temperature at the surface of the lithographic printing plate precursor) is about 55 ° C., and is preferably set in the range of 50 to 60 ° C. However, this set temperature can be appropriately set according to the configuration of the lithographic printing plate precursor and the prescription of the developer.

  Further, the developing device 1 includes a replenishing unit 60 and a liquid feeding device.

  The replenishment unit 60 replenishes the tank 30 of the second processing unit 3 with fresh developer via a pipe or the like. The fresh replenisher is an unused developer that has not processed the plate, and is preferably an unused developer L2.

  The liquid feeding device feeds an amount of the developer corresponding to the state of the developer L1 stored in the tank 20 of the first processing unit 2 from the tank 30 of the second processing unit 3 to the tank 20. The liquid feeding device includes a pipe 80, a recovery unit 82, a tank 84, and a pump 86.

  The pipe 80 extends between the tank 20 and the tank 30 and is a closed circuit through which the developer L2 to be fed is circulated.

  When the developer L2 stored in the tank 30 exceeds a certain liquid level, the recovery unit 82 recovers an amount of developer L2 corresponding to the amount exceeding the recovery port, and guides it into the pipe 80.

  The tank 84 is connected to the recovery unit 82 via a pipe 80. The tank 84 temporarily stores the developer L2 collected by the collection unit 82.

  The pump 86 is connected to the tank 84 via a pipe 80. The pump 86 sends the developer L2 stored in the tank 84 to the tank 20 of the first processing unit 2 via the pipe 80. The pump 86 feeds the developer L2 to the tank 20 with a liquid feeding amount corresponding to the rotational speed by controlling the rotational speed of the drive motor. The pump 86 can supply, for example, a predetermined volume of developer, and for example, a bellows pump, a diaphragm pump, a piston pump, a plunger pump, or the like can be employed.

  Further, the liquid feeding device may include a filter unit for removing foreign matters such as debris contained in the developer L2 in the pipe. In this way, residue etc. can be removed from the developing solution, and the developing solution can always be kept clean. Furthermore, the collection part 82 and the tank 84 may be provided integrally.

  The developing device 1 can replenish the tank 30 of the second processing unit 3 with the fresh developer L2 by the replenishing unit 60. For this reason, it can suppress that the state of the developing solution L2 stored in the tank 30 deteriorates.

  Further, the developing device 1 replenishes the developer L2 from the tank 30 to the tank 20 by the liquid feeding device in accordance with the state of the developer stored in the first tank. The state of the developer stored in the first tank is the level (liquid level) of the developer L1 and the fatigue level of the developer L1.

  The developer L1, the developer L2, and the developer L3 may have the same or different compositions as long as the effects of the present invention are not impaired. It is preferable to use the same developer L1 and developer L2. In this case, the developing device 1 supplies the developer L2 fed to the tank 20 by the liquid feeder so that the component of the developer L1 stored in the tank 20 of the first processing unit 2 does not change and is stable. The amount of control. The temperatures of the developers L1 and L2 can be used at any temperature, but are preferably 10 ° C to 50 ° C.

  Further, in order to restore the developability of the developer L1 stored in the tank 20, a concentrated liquid may be used as the developer L2 replenished in the tank 30 of the second processing unit 3. When the concentrate is replenished, the tank 84 is shielded and the evaporation amount is small. The replenishment amount at this time is preferably 1.05 to 6 times, more preferably 1.1 to 3 times, and still more preferably 1.1 to 2 times. On the other hand, the developer L2 is likely to come into contact with the outside air and the evaporation may be large. In this case, the liquid to be replenished may be on the dilution side. In this case, it is preferably 0.6 to 0.95 times, more preferably 0.7 to 0.9 times, and still more preferably 0.8 to 0.9 times.

  The amount of liquid fed from the tank 30 to the tank 20 is preferably set to 1 L / min or less in order to prevent the temperature uniformity from being locally impaired when the amount of liquid fed is increased.

  The tank 30 is provided with a liquid circulation spray (not shown), and the accumulated developer L1 is circulated by a circulation pump (not shown) to maintain the uniformity of the developer L1. .

  The developing device 1 is a system in which an amount corresponding to the amount increased by the replenishment of the replenishing unit 60 is collected from the collecting unit 82 and stored in the tank 84 and then fed. However, the liquid feeding method is not limited to this. In anticipation of a change in the state of the developer L1 stored in the tank 20, a predetermined amount of developer may be fed.

  According to the developing device 1, the replenishment unit 60 replenishes the second processing unit 3, thereby preventing the developer L <b> 2 stored in the tank 30 from deteriorating. Further, the developer L2 can be fed from the tank 30 to the tank 20 by the liquid feeding device. For this reason, there is no need to provide a mechanism for replenishing the developer in the tank 20, and a predetermined amount can be fed to the tank 20 according to the state of the developer L1, and the amount of liquid fed by the pump 86 is accurately controlled. can do. For this reason, the state of the developer can be maintained, and a lithographic printing plate can be stably produced with high quality.

  Further, since the developing device 1 sends the developer L2 to the tank 20 via the pipe 80 that is a closed circuit, it is possible to prevent the developer L2 being sent from being altered due to the influence of evaporation or the like. In the configuration in which the developer stored in the tank is overflowed and the developer is supplied to the tank, it is impossible to control the amount of the developer to be fed and the deterioration of the developer is remarkable.

  Further, the developing device 1 can perform liquid feeding even when another processing unit exists between the first processing unit 2 and the second processing unit 3.

  Next, another example of the configuration of the developing device will be described. FIG. 2 is a schematic diagram illustrating another configuration example of the developing device.

  The developing device 1 in this example is basically the same as the developing device shown in FIG. About the structure and member already demonstrated, description is abbreviate | omitted or simplified by attaching | subjecting the same reference number.

  The developing device 1 includes a first processing unit 2, a second processing unit 3, and a third processing unit 4 in order from the upstream side in the transport path of the planographic printing plate precursor 10.

  The developer L1 is stored in the tank 20 of the second processing unit 3. Wash water W is stored in the tank 30 of the second processing unit 3. The developer L2 is stored in the tank 40 of the third processing unit 4. The first processing unit 2 functions as a first developing unit, and the third processing unit 4 functions as a second developing unit. Moreover, the 2nd process part 3 functions as a washing part.

  The developing device 1 performs development by transporting the transported lithographic printing plate precursor 10 while immersing it in the developer L1 stored in the tank 20 of the first processing unit 2. Thereafter, the lithographic printing plate precursor 10 is washed with water by the second processing unit 3, and the developer L 2 is sprayed from the spray tube 41 onto the lithographic printing plate precursor by the third processing unit 4. The image recording layer in the undeveloped area is supplementarily developed.

  The developing device 1 includes a replenishing unit 60 that replenishes the tank 40 of the third processing unit 4 with the developer L2.

  Further, the developing device 1 includes a liquid feeding device. The liquid feeding device feeds the developer in an amount corresponding to the state of the developer L1 stored in the tank 20 from the tank 40 to the tank 20. The configuration of the liquid feeding device is the same as that described above.

  As shown in FIG. 2, even if there is a water washing unit (second processing unit 3) between the first processing unit 2 and the third processing unit 4, the liquid feeding device supplies the liquid to the tank 20. Is possible. For this reason, the developing device 1 can send and replenish the developer regardless of the number and arrangement of the processing units, and keep the developers L1 and L2 in a good state. be able to.

  In addition, the 2nd process part 3 is good also as a process part which performs processes other than a washing part. Further, another processing unit may be provided on the downstream side of the conveyance path of the third processing unit 4.

  The configuration of the developing device 1 described above can be changed as appropriate.

  For example, although the 2nd processing part 3 and the 3rd processing part were made into the horizontal conveyance system, an effect can be expressed also with an immersion system.

  For example, the developing device includes three tanks 20, 30, and 40, but is not limited thereto. The developing device 1 may include four or more tanks.

  The developing device is a so-called disposable process in which a developer stored in a tank is pumped up and sprayed from a nozzle, or a substantially unused processing solution is supplied for each plate and developed. Any of the methods is generally used. From the viewpoint of preventing the liquid from scattering, a method of developing the lithographic printing plate precursor by dipping and transporting it is excellent.

  The developing device may further include an exposure device.

  In the present invention, a lithographic printing plate precursor after development (hereinafter referred to as a lithographic printing plate) can optionally be subjected to a desensitization treatment. In the 1st process part 2 and the 2nd process part 3, you may perform a desensitization process simultaneously with image development.

  Next, the developer will be described. In order to enable the desensitization treatment simultaneously with development, a developer having the following constitution can be preferably used. In particular, it is preferable to contain at least one of a surfactant and a water-soluble polymer compound, which will be described later, from the viewpoint of imparting a desensitizing treatment ability.

  The developer used in the lithographic printing plate preparation method of the present invention is preferably an aqueous solution containing water as a main component (containing 60% by mass or more of water). The pH of the developer is preferably 2.0 or more and less than 10.0, more preferably 5.0 or more and less than 10.0, still more preferably 6.0 or more and less than 10.0, and most preferably 6.9 or more. It is 9.9 or less.

  The developer may contain an alkali agent. In the case of containing an alkali agent, it is a preferred embodiment that the pH is 8.0 or more and less than 10.0, more preferably 9.0 or more and less than 10.0, and still more preferably 9.2 or more and 9 .9 or less. In the case of not containing an alkaline agent, the pH is preferably 2.0 or more and 9.0 or less, more preferably 4.0 or more and 8.0 or less, and further preferably 4.5 or more and 7 or less. .5 or less.

  The developer used in the present invention preferably contains a surfactant. In this case, examples of the surfactant used include anionic, cationic, nonionic, and zwitterionic types.

  The anionic surfactant is not particularly limited, but fatty acid salts, abietic acid salts, hydroxyalkane sulfonic acid salts, alkane sulfonic acid salts, dialkyl sulfosuccinic acid salts, linear alkyl benzene sulfonic acid salts, branched alkyl benzene sulfonic acid salts. Alkyl naphthalene sulfonates, alkyl diphenyl ether (di) sulfonates, alkylphenoxy polyoxyethylene propyl sulfonates, polyoxyethylene alkyl sulfophenyl ether salts, N-methyl-N-oleyl taurine sodium, N-alkyl sulfosuccinates Acid monoamide disodium salts, petroleum sulfonates, sulfated castor oil, sulfated beef tallow oil, sulfate esters of fatty acid alkyl esters, alkyl sulfate esters, polio Siethylene alkyl ether sulfates, fatty acid monoglyceride sulfates, polyoxyethylene alkylphenyl ether sulfates, polyoxyethylene styryl phenyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxy Examples thereof include ethylene alkylphenyl ether phosphoric acid ester salts, saponification products of styrene-maleic anhydride copolymer, partial saponification products of olefin-maleic anhydride copolymer, and naphthalene sulfonate formalin condensates. Among these, alkylbenzene sulfonates, alkyl naphthalene sulfonates, and alkyl diphenyl ether (di) sulfonates are particularly preferably used.

  The cationic surfactant is not particularly limited, and examples thereof include alkylamine salts, quaternary ammonium salts, polyoxyethylene alkylamine salts, and polyethylene polyamine derivatives.

  The nonionic surfactant is not particularly limited, but is a polyethylene glycol type higher alcohol ethylene oxide adduct, alkylphenol ethylene oxide adduct, alkyl naphthol ethylene oxide adduct, phenol ethylene oxide adduct, naphthol ethylene oxide adduct, Fatty acid ethylene oxide adduct, polyhydric alcohol fatty acid ester ethylene oxide adduct, higher alkylamine ethylene oxide adduct, fatty acid amide ethylene oxide adduct, fat and oil ethylene oxide adduct, polypropylene glycol ethylene oxide adduct, dimethylsiloxane-ethylene oxide Block copolymer, dimethylsiloxane- (propylene oxide-ethylene oxide) block copoly , Fatty acid ester of glycerol of polyhydric alcohol type, fatty acid ester of pentaerythritol, fatty acid ester of sorbitol and sorbitan, fatty acid ester of sucrose, alkyl ether of polyhydric alcohol, fatty acid amide of alkanolamines, etc. . Among these, those having an alkylene oxide chain are preferred, those having an aromatic ring and an ethylene oxide chain are more preferred, alkyl-substituted or unsubstituted phenol ethylene oxide adducts, or alkyl-substituted or unsubstituted naphthol ethylene oxide adducts Is more preferable.

  The nonionic surfactant having an alkylene oxide chain is particularly preferably a nonionic aromatic ether surfactant represented by the following general formula (3).

X-Y-O- (A) n- (B) m-H (3)
In formula (3), X represents an aromatic group, Y represents a single bond or an alkylene group having 1 to 10 carbon atoms, A and B are groups different from each other, and represent —CH ₂ CH ₂ O— or — CH ₂ CH (CH ₃ ) O— is represented, and n and m each represents an integer of 0 to 100, provided that the sum of n and m is 2 or more.

  In the formula (3), examples of the aromatic group represented by X include a phenyl group, a naphthyl group, and an anthranyl group. The aromatic group may have a substituent. Examples of the substituent include an organic group having 1 to 100 carbon atoms. Examples of the organic group are the same as the examples of the organic group described for the following general formulas (3-A) and (3-B). In Formula (3), when both A and B are present, they may be present randomly or as a block. Moreover, 4-100 are preferable, as for the sum of n and m, 6-50 are more preferable, 8-30 are still more preferable, and 10-28 are especially preferable.

  Of the nonionic aromatic ether surfactants represented by the general formula (3), a compound represented by the following general formula (3-A) or (3-B) is preferable.

In formulas (3-A) and (3-B), R ₁₀ and R ₂₀ each represent a hydrogen atom or an organic group having 1 to 100 carbon atoms, t and u each represent 1 or 2, Y1, Y2 Each represents a single bond or an alkylene group having 1 to 10 carbon atoms, v and w each represents an integer of 0 to 100, provided that the sum of v and w is 2 or more, and v ′ and w ′ are each 0 to Represents an integer of 100, provided that the sum of v ′ and w ′ is 2 or more.

When t is 2 and R ₁₀ is an organic group having 1 to 100 carbon atoms, R ₁₀ may be the same or different, or R 10 together may form a ring, When u is 2 and R ₂₀ is an organic group having 1 to 100 carbon atoms, R ₂₀ may be the same or different, or R ₂₀ together may form a ring.

  Specific examples of the organic group having 1 to 100 carbon atoms include an aliphatic hydrocarbon group, an aromatic hydrocarbon group (for example, an alkyl group, an alkenyl group, an alkynyl group) which may be saturated or unsaturated, and may be linear or branched. , Aryl groups, aralkyl groups, etc.), alkoxy groups, aryloxy groups, N-alkylamino groups, N, N-dialkylamino groups, N-arylamino groups, N, N-diarylamino groups, N-alkyl-N-aryls Amino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyl Oxy group, acylamino group, N-alkylacylamino group, N-arylacyl Mino group, acyl group, alkoxycarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group , N-alkyl-N-arylcarbamoyl groups, polyoxyalkylene chains, and the above organic groups to which a polyoxyalkylene chain is bonded. The alkyl group may be linear or branched.

Preferred examples of R ₁₀ and R ₂₀ include a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkoxycarbonyl group, an N-alkylamino group, N, N— Dialkylamino group, N-alkylcarbamoyl group, acyloxy group, acylamino group, polyoxyalkylene chain having 5 to 20 repeating units, aryl group having 6 to 20 carbon atoms, polyoxyalkylene chain having 5 to 20 repeating units An aryl group to which is bonded.

  In the compound represented by the general formula (3-A) or (3-B), the number of repeating units of the polyoxyethylene chain is preferably 3 to 50, more preferably 5 to 30. The number of repeating units of the polyoxypropylene chain is preferably 0 to 10, more preferably 0 to 5. The polyoxyethylene part and the polyoxypropylene part may be present randomly or as a block.

  Specific examples of the nonionic aromatic ether activator represented by the general formula (3) are shown below, but the present invention is not limited thereto.

The zwitterionic surfactant is not particularly limited, and examples thereof include amine oxides such as alkyldimethylamine oxide, betaines such as alkylbetaines, and amino acids such as alkylamino fatty acid sodium.
In particular, alkyldimethylamine oxide which may have a substituent, alkylcarboxybetaine which may have a substituent, and alkylsulfobetaine which may have a substituent are preferably used. Specific examples thereof include those described in JP-A-2008-203359 [0255] to [0278], JP-A-2008-276166 [0028] to [0052], and the like.

  As the zwitterionic surfactant used in the developer, a compound represented by the following general formula (1) or a compound represented by the general formula (2) is preferable.

In formulas (1) and (2), R ¹ and R ¹¹ each independently represent an alkyl group having 8 to 20 carbon atoms or a linking group having 8 to 20 carbon atoms in total.
R ² , R ³ , R ¹² and R ¹³ each independently represents a group containing a hydrogen atom, an alkyl group or an ethylene oxide group.
R ⁴ and R ¹⁴ each independently represents a single bond or an alkylene group.
Further, two groups out of R ¹ , R ² , R ³ and R ⁴ may be bonded to each other to form a ring structure, and two groups out of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are They may combine to form a ring structure.

In the compound represented by the general formula (1) or the compound represented by the general formula (2), when the total carbon number increases, the hydrophobic portion increases and the solubility in an aqueous developer decreases. In this case, the solubility is improved by mixing an organic solvent such as alcohol that aids dissolution into water as a dissolution aid, but if the total carbon number becomes too large, the surfactant is within the proper mixing range. Can not be dissolved. Therefore, the total number of carbon atoms of R ^{1 to} R ⁴ or R ^{11 to} R ¹⁴ is preferably 10 to 40, more preferably 12 to 30.

The alkyl group having a linking group represented by R ¹ or R ¹¹ represents a structure having a linking group between the alkyl groups. That is, when there is one linking group, it can be represented by “-alkylene group-linking group-alkyl group”. Examples of the linking group include an ester bond, a carbonyl bond, and an amide bond. There may be two or more linking groups, but one is preferable, and an amide bond is particularly preferable. The total number of carbon atoms of the alkylene group bonded to the linking group is preferably 1 to 5. The alkylene group may be linear or branched, but is preferably a linear alkylene group. The alkyl group bonded to the linking group preferably has 3 to 19 carbon atoms, and may be linear or branched, but is preferably linear alkyl.

When R ² or R ¹² is an alkyl group, the number of carbon atoms is preferably 1 to 5, and particularly preferably 1 to 3. Either a straight chain or a branched chain may be used, but a straight chain alkyl group is preferable.

When R ³ or R ¹³ is an alkyl group, the carbon number is preferably 1 to 5, and particularly preferably 1 to 3. Either a straight chain or a branched chain may be used, but a straight chain alkyl group is preferable.
Examples of the group containing an ethylene oxide represented by R ³ or ^{R 13,} can be a group represented by -Ra (CH2CH2O) nRb. Here, Ra represents a single bond, an oxygen atom or a divalent organic group (preferably having 10 or less carbon atoms), Rb represents a hydrogen atom or an organic group (preferably having 10 or less carbon atoms), and n is 1 to 10 Represents an integer.

When R ⁴ and R ¹⁴ are alkylene groups, the number of carbon atoms is preferably 1 to 5, and particularly preferably 1 to 3. Either a straight chain or a branched chain may be used, but a linear alkylene group is preferable.
The compound represented by the general formula (1) or the compound represented by the general formula (2) preferably has an amide bond, and more preferably has an amide bond as a linking group for R ¹ or R ¹¹ .
Representative examples of the compound represented by the general formula (1) or the compound represented by the general formula (2) are shown below, but the present invention is not limited thereto.

  The compound represented by the formula (1) or (2) can be synthesized according to a known method. Moreover, it is also possible to use what is marketed. As a commercially available product, examples of the compound represented by the formula (1) include SOFTAZOLINE LPB, SOFTAZOLINE LPB-R, Vista MAP, Takesurf Oil & Chemicals Takesurf C-157L manufactured by Kawaken Fine Chemicals. Examples of the compound represented by the formula (2) include SOFTAZOLIN LAO manufactured by Kawaken Fine Chemical Co., Ltd., Amorgen AOL manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and the like.

  Two or more surfactants may be used, and the content of the surfactant in the developer is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass.

  The developer according to the present invention preferably contains a water-soluble polymer compound having film-forming properties for the purpose of assisting desensitization of non-image areas and plate surface protection.

  Examples of the water-soluble polymer compound include gum arabic, fiber derivatives (eg, carboxymethylcellulose, carboxyethylcellulose, methylcellulose, hydroxypropylcellulose, methylpropylcellulose, etc.) and modified products thereof, polyvinyl alcohol and derivatives thereof, polyvinylpyrrolidone, Polyacrylamide, vinyl methyl ether / maleic anhydride copolymer, vinyl acetate / maleic anhydride copolymer, styrene / maleic anhydride copolymer, starch derivatives (eg, dextrin, maltodextrin, enzymatic degradation dextrin, hydroxypropylated) Starch, hydroxypropylated starch, enzymatically decomposed dextrin, carboxydimethylated starch, phosphorylated starch, cyclodextrin, etc.), pullulan and derivatives thereof.

  Other starch derivatives that can be used as water-soluble polymer compounds include roasted starch such as British gum, enzyme-modified dextrins such as enzyme dextrin and shardinger dextrin, oxidized starch shown in solubilized starch, and modified alpha-formation Pregelatinized starch such as starch and unmodified pregelatinized starch, phosphate starch, fat starch, sulfate starch, nitrate starch, xanthate starch and carbamate starch, carboxyalkyl starch, hydroxyalkyl starch, sulfoalkyl starch Etherified starch such as cyanoethyl starch, allyl starch, benzyl starch, carbamylethyl starch, dialkylamino starch, cross-linked starch such as methylol cross-linked starch, hydroxyalkyl cross-linked starch, phosphoric acid cross-linked starch, dicarboxylic acid cross-linked starch, starch polyacryloamyl Copolymer, starch polyacrylic acid copolymer, starch polyvinyl acetate copolymer, starch polyacrylonitrile copolymer, chaotic starch polyacrylic ester copolymer, chaotic starch vinyl polymer copolymer, starch polystyrene malee Examples thereof include starch graft polymers such as acid copolymers, starch polyethylene oxide copolymers, and starch polypropylene copolymers.

Examples of natural polymer compounds that can be used as water-soluble polymer compounds include water-soluble soybean polysaccharides, starch, gelatin, hemicellulose extracted from soybeans, potato starch, potato starch, tapioca starch, wheat starch, and corn starch. Starch, Carrageenan, Laminaran, Sea Saumannan, Funari, Irish Moss, Agar, Algae, etc. , Plant mucous substances such as benzoin gum, homopolysaccharides such as dextran, glucan and levan, and microbial mucous substances such as hetropolysaccharides such as succinoglucan and santangum, glue, gelatin, casein and Proteins such as collagen and the like.
Among them, gum arabic, starch derivatives such as dextrin and hydroxypropyl starch, carboxymethyl cellulose, soybean polysaccharide and the like can be preferably used.
The content of the water-soluble polymer compound in the developer is preferably 0.05 to 15% by mass, and more preferably 0.5 to 10% by mass.

The developer used in the present invention preferably further contains a pH buffer.
As the pH buffering agent of the present invention, a buffering agent that exhibits a buffering action at a pH of 2.0 to 10.0 is preferable, and a weak alkaline pH buffering agent is more preferably used. Specific examples include (a) carbonate ions and hydrogen carbonate ions, (b) borate ions, (c) organic amine compounds and ions of the organic amine compounds, and combinations thereof. That is, for example, (a) a combination of carbonate ion and hydrogen carbonate ion, (b) borate ion, or (c) a combination of an organic amine compound and an ion of the organic amine compound exhibits a pH buffering action in the developer. Further, even when the developer is used for a long period of time, fluctuations in pH can be suppressed, and development deterioration due to fluctuations in pH, generation of development residue, and the like can be suppressed. Particularly preferred are (a) a combination of carbonate ions and hydrogencarbonate ions and (c) an organic amine compound and ions of the organic amine compound.

  In order to allow carbonate ions and hydrogen carbonate ions to be present in the developer, carbonate and hydrogen carbonate may be added to the developer, or by adjusting the pH after adding carbonate or bicarbonate, Ions and bicarbonate ions may be generated. The carbonate and bicarbonate are not particularly limited, but are preferably alkali metal salts. Examples of the alkali metal include lithium, sodium, and potassium, and sodium is particularly preferable. These may be used alone or in combination of two or more.

  When (a) a combination of carbonate ions and bicarbonate ions is employed as the pH buffer, the total amount of carbonate ions and bicarbonate ions is preferably 0.05 to 5 mol / L with respect to the developer, and 0.1 to 2 mol. / L is more preferable, and 0.2 to 1 mol / L is particularly preferable. When the total amount is 0.05 mol / L or more, developability and processing ability are hardly lowered, and when it is 5 mol / L or less, it is difficult to form precipitates and crystals. It is difficult to gel, and it is difficult to cause waste liquid treatment.

  When (b) borate ions are employed as the pH buffering agent, the total amount of borate ions is preferably 0.05 to 5 mol / L, more preferably 0.1 to 2 mol / L with respect to the developer. 2-1 mol / L is particularly preferable. When the total amount of borate is 0.05 mol / L or more, developability and processing ability are hardly lowered, and when it is 5 mol / L or less, it is difficult to form precipitates and crystals. It becomes difficult to gel during neutralization, and the waste liquid treatment is unlikely to be hindered.

In the present invention, a combination of a water-soluble amine compound and an ion of the amine compound can also be preferably used.
The water-soluble amine compound is not particularly limited, but a water-soluble amine compound having a group that promotes water solubility is preferable. Examples of groups that promote water solubility include carboxylic acid groups, sulfonic acid groups, sulfinic acid groups, phosphonic acid groups, and hydroxyl groups. The water-soluble amine compound may have a plurality of groups that promote water solubility. The carboxylic acid group, sulfonic acid group, sulfinic acid group, and phosphonic acid group may have a salt structure. Of these, amine compounds having a hydroxyl group are particularly preferred.

  Specific examples of water-soluble amine compounds having a carboxylic acid group, a sulfonic acid group, and a sulfinic acid group include glycine, aminodiacetic acid, lysine, threonine, serine, aspartic acid, parahydroxyphenylglycine, dihydroxyethylglycine, alanine, Examples include amino acids such as anthranilic acid and tryptophan, sulfamic acid, cyclohexylsulfamic acid, fatty acid amine sulfonic acid such as taurine, fatty acid amine sulfinic acid such as aminoethanesulfinic acid, and sodium, potassium, and ammonium salts thereof. . Of these, glycine, aminodiacetic acid and salts thereof are preferable.

  Specific examples of water-soluble amine compounds having a phosphonic acid group (including a phosphinic acid group) include 2-aminoethylphosphonic acid, 1-aminoethane-1, 1-diphosphonic acid, 1-amino-1-phenylmethane-1. 1-diphosphonic acid, 1-dimethylaminoethane-1, 1-diphosphonic acid, ethylenediaminopentamethylenephosphonic acid, and sodium, potassium and ammonium salts thereof. Of these, 2-aminoethylphosphonic acid and salts thereof are preferred.

Specific examples of the water-soluble amine compound having a hydroxyl group include monoethanolamine, diethanolamine, triethanolamine, N-hydroxyethylmorpholine, monoisopropanolamine, monoisopropanolamine, diisopropanolamine, diisopropanolamine, triisopropanolamine. , Triisopropanolamine N, N-diethanolaniline and the like. Of these, monoethanolamine, diethanolamine, triethanolamine, and N-hydroxyethylmorpholine are preferable.
Of these, di- or trialkanolamine compounds and ions thereof substituted with an alkyl group having at least one hydroxyl group are particularly preferable. The alkyl group having at least one hydroxyl group may further have a substituent selected from another hydroxyl group, halogen, nitro group, nitrile group, (hetero) aromatic group, saturated or unsaturated hydrocarbon group. good. The alkyl group preferably has 15 or less carbon atoms, more preferably 12 or less carbon atoms, and still more preferably 8 or less carbon atoms.

Specific alkanol groups include HO—CH ₂ — *, HO—CH ₂ —CH ₂ — *, HO—CH ₂ —CH ₂ —CH ₂ — *, CH ₃ —CH (OH) —CH ₂ — *. _{, CH 3 -C (OH) (} CH 3) - *, HO-CH 2 -CH 2 -CH 2 -CH 2 - *, CH 3 -CH (CH 3) -CH (OH) - *, CH 3 - _{CH (C 2 H 5) -CH} (OH) - *, CH 3 -C (CH 3) (OH) -CH 2 - *, HO-CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH _{2 - *, HO-CH 2} -CH 2 -CH 2 -CH (OH) -CH 2 -CH 2 - *, CH 3 -CH 2 -CH (OH) -CH 2 -CH 2 -CH 2 - *, _{CH 3 -CH (CH 3) -CH} 2 -CH (OH) -CH 2 - *, CH 3 -CH (C 2 H _{) -CH 2 -CH (OH) -CH} 2 - *, HO-CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 - *, HO-CH 2 -CH 2 _{-CH 2 -CH (OH) -CH 2} -CH 2 -CH 2 -CH 2 - *, CH 3 -CH 2 -CH (OH) -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 - * _{, CH 3 -CH (CH 3)} -CH 2 -C (C 2 H 5) (OH) -CH 2 -CH 2 -CH 2 - *, and the like. (Here, * indicates the connecting part of the amine group to N.)

  Specific examples of the di- or trialkanolamine include triethanolamine, diethanolamine, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, and trishydroxymethylamino. And methane and triisopropanolamine.

  The ion of the water-soluble amine compound can be generated in an aqueous solution of the water-soluble amine compound, and an alkali or an acid may be further added to the aqueous solution of the water-soluble amine compound. Can be contained in the aqueous solution.

  Examples of the alkali that can be used include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, and combinations thereof. As the acid, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, phosphorous acid and the like can be used, and phosphoric acid and phosphorous acid are particularly preferable. The pH can be finely adjusted by adding such an alkali or acid.

  The developer according to the present invention preferably contains a salt composed of a reaction product of an acid and an amine, whereby an ion of an organic amine compound is generated.

  More preferably, the developer contains a salt composed of a reaction product of at least one of phosphoric acid and phosphorous acid and a di- or trialkanolamine.

  When c) an organic amine compound and ions of the organic amine compound are used as the pH buffer, the content is preferably 0.005 to 5 mol / L in terms of molar concentration in the developer, and 0.01 to 2 mol / L is more preferable, and 0.01 to 1 mol / L is particularly preferable. When the total amount of ions of the water-soluble amine compound is within this range, the developability and processing ability are not lowered, while the waste liquid treatment is easy.

  When the pH buffer is a salt composed of a reaction product of at least one of phosphoric acid and phosphorous acid and a di- or trialkanolamine, the content thereof is at least 0.00 mol in terms of molar concentration in the developer. 02 mol / L is preferred, at least 0.1 mol / L is more preferred, and at least 0.15 mol / L is particularly preferred. Moreover, 5 mol / L or less is preferable, 2.5 mol / L or less is more preferable, and 1 mol / L or less is especially preferable. The substance amount ratio of amine to acid is preferably 0.1 or more, more preferably 0.4 or more, and most preferably 0.75 or more. Moreover, 20 or less is preferable, 12 or less is more preferable, and 5 or less is still more preferable.

  The developer according to the present invention may contain an organic solvent. Examples of the organic solvent that can be contained include aliphatic hydrocarbons (hexane, heptane, isoper E, H, G (manufactured by Esso Chemical Co., Ltd.)), aromatic hydrocarbons (toluene, xylene, etc.), halogenated carbons. Examples include hydrogen (methylene dichloride, ethylene dichloride, trichlene, monochlorobenzene, etc.) and polar solvents. Examples of polar solvents include alcohols (methanol, ethanol, propanol, isopropanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, 1 -Nonanol, 1-decanol, benzyl alcohol, ethylene glycol monomethyl ether, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl Ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether Ter, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, etc.), ketones (acetone, methyl ethyl ketone, ethyl butyl ketone, methyl isobutyl ketone) , Cyclohexanone, etc.), esters (ethyl acetate, propyl acetate, butyl acetate, amyl acetate, benzyl acetate, methyl lactate, butyl lactate, ethylene glycol monobutyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol acetate, diethyl phthalate, butyl levulinate Etc.), others (triethyl phosphate, tricresyl phosphate, N-phenylethanolamine) , N- phenyldiethanolamine, N- methyldiethanolamine, N- ethyldiethanolamine, 4- (2-hydroxyethyl) morpholine, N, N- dimethylacetamide, N- methylpyrrolidone and the like) and the like.

  Two or more organic solvents can be used in combination in the developer. When the organic solvent is insoluble in water, it can be used after being solubilized in water using a surfactant or the like. From the viewpoint of safety and flammability, the concentration of the organic solvent is preferably less than 40% by mass, preferably less than 10% by mass, and more preferably less than 5% by mass.

  The developer according to the present invention may contain an enzyme. The enzyme used in the present invention is not particularly limited as long as it has an action of suppressing the development of development residue in the development processing of a lithographic printing plate precursor having a photopolymerizable image recording layer. Tatsuhiko Yagi Any enzyme can be used as long as it is a group of enzymes as described in “Enzyme Handbook (3rd Edition)” (Asakura Shoten). In particular, for the purpose of decomposing and solubilizing monomers (ethylenically unsaturated compounds), EC3. Of the enzyme number (EC number) of the International Biochemical Molecular Biology Union (IUBMB) Enzyme Committee. It is preferable to use hydrolases belonging to the group. In many cases, ethylenically unsaturated compounds are composed of carbon atoms, hydrogen atoms, nitrogen atoms, oxygen atoms, sulfur atoms, phosphorus atoms, halogen atoms, etc. Enzymes that hydrolyze esters, enzymes that hydrolyze sulfate esters, enzymes that hydrolyze ether bonds, enzymes that hydrolyze thioether structures, enzymes that hydrolyze peptide bonds, enzymes that hydrolyze carbon-nitrogen bonds, carbon -Enzymes that hydrolyze carbon bonds, enzymes that hydrolyze carbon-halogen bonds, etc. are mentioned as preferred enzymes, more preferably ester bonds, amide bonds, tertiary amino groups, urethane bonds, urea bonds, thiourethane bonds. And an enzyme that hydrolyzes at least one selected from the group consisting of thiourea bonds.

  Among these, those belonging to the EC 3.1 group (ester hydrolase) and the EC 3.4 group (peptide bond hydrolase) are particularly preferable, and EC 3.1.1.3 (triacylglycerol lipase) and EC 3.4 are preferable. .11.1 (leucine aminopeptidase), EC 3.4.21.62 (subtilisin), EC 3.4.21.63 (oryzin), EC 3.4.22.2 ( Papain), EC 3.4.22.32 (stem bromelain), EC 3.4.2.18 (aspergillo pepsin I), EC 3.4.224.25 (vibriolysin), EC 3.4.24.27 (Thermolysin) And, EC3.4.24.28 (bacillolysin (bacillolysin)) are preferable. Further, EC 3.1.1.3, EC 3.4.21.14, EC 3.4.21.62, and EC 3.4.21.63 are most preferable.

  Furthermore, as described above, in the present invention, the pH of the developer is preferably 2.0 to 10.0, more preferably 5.0 to 10.0, still more preferably 6.0 to 10.0, Most preferably, it is 6.9-9.9.

  From these viewpoints, an alkaline enzyme is preferably used as the enzyme. Here, the alkaline enzyme is an enzyme whose alkaline pH range is alkaline, preferably an enzyme having an optimal pH range of 6.9 to 9.9, and an enzyme having an optimal temperature range of 20 ° C to 60 ° C. Preferably, an enzyme having 25 ° C to 50 ° C is more preferable.

  Specifically, an enzyme capable of mainly hydrolyzing the ester group of the monomer under alkaline conditions, such as alkaline protease and alkaline lipase, is preferred. Alkaline proteases include Bacillus subtilis, Aspergillus oryzae, Bacillus stearothermophilus, papaya latex, papaya, Ananas comosmus M, Pig pancreasluspirus, Bacillus lichenisperformus, Bacillus lentus, Bacillus sp. , Bacillus clausii, alkaline lipase include Candida cylindracea, Humicola langinosa, Psudomonas, Mucor sp. , Chromobacteria viscosum, Rhizopus japonics, Aspergillus niger, Mucor javanicus, Penicillium camemberti, Rhizopus oryzae, Candida rugis. , Aspergillus sp. Rhizomucor miehei, Bacillus sp. Alcaligenes sp. There are things of microbial origin such as.

  As more specific embodiments, lipase PL, lipase QLM, lipase SL, lipase MY, lipase OF (manufactured by Meikatsu Sangyo Co., Ltd.), Neulase F3G, lipase A “Amano” 6, lipase AY “Amano” 30G Lipase G “Amano” 50, Lipase R “Amano”, Lipase AS “Amano”, Umamizyme G, Papain W-40, Protease A “Amano” G, Protease N “Amano” G, Protease NL “Amano”, Protease P “Amano” 3G, Protease S “Amano” G, Promeline F, Proleather FG-F, Peptidase R, Samoaase PC10F, Protin SD-AC10F, Protin SD-AY10, Protin SD-PC10F, Protin SD-NY10, Pancreatic Digestive enzyme TA, prozyme, prozyme 6, se Alkaline proteinase, lipase AYS “Amano”, lipase PS “Amano” SD, lipase AK “Amano”, lipase PS “Amano” IM, protease N “Amano”, protease S “Amano”, acylase “Amano”, D-aminoacylase “Amano” etc. (above, manufactured by Amano Enzyme Co., Ltd.), Alcalase, Esperase, Sabinase, Everase, Cannase, Lipolase, Lipex, NS44020, NS44120, NS44060, NS44114, NS44126, NS44160, etc. (above Novozymes Japan) Manufactured), alkaline protease (manufactured by Takeda Chemical Industry Co., Ltd.), Aroase XA-10 (Yakult Pharmaceutical Co., Ltd.), alkaline protease GL, Protex 6L, Purefect, Purefect OX, Properase, Protex OXG, Protex 40L (Genencor Kyowa Co., Ltd.), Sumiteam MP (Shin Nihon Chemical Industry Co., Ltd.), Biobrase OP, Biobrase AL-15KG, Biobrase 30G, Biobrase APL-30, Biobrase XL-416F Biolase SP-20FG, Biolase SP-4FG, Protease CL-15 (Nagase ChemteX Co., Ltd.), Orientase (HIBI Co., Ltd.), Entilon SA (Santo Kasei Kogyo Co., Ltd.) and the like.

As a method for introducing these enzymes, they may be introduced directly into the developer or at the time of lithographic printing plate processing. Moreover, you may perform a development process, supplying an enzyme to a developing solution.
The content of the enzyme used is preferably 0.01% by weight to 20% by weight, more preferably 0.1% by weight to 10% by weight, and more preferably 0.2% by weight to 5% by weight with respect to the total amount of the developer. Most preferred.

  In addition to the above components, the developer may contain a preservative, a chelate compound, an antifoaming agent, an organic acid, an inorganic acid, an inorganic salt, and the like. Specifically, compounds described in paragraph numbers [0266] to [0270] of JP-A-2007-206217 can be preferably used.

  The developer according to the present invention can be used as a developer for an exposed lithographic printing plate precursor and, if necessary, a developer replenisher. Further, it can be preferably applied to the automatic developing processor as described above. When developing using an automatic developing processor, the developing solution becomes fatigued according to the amount of processing, so that the processing capability may be restored by using a replenishing solution or a fresh developing solution.

  In the method for preparing a lithographic printing plate according to the present invention, the entire lithographic printing plate precursor may be heated before exposure, during exposure, and between exposure and development, if necessary. Such heating promotes an image forming reaction in the image recording layer, and has advantages such as improvement in sensitivity, printing durability, and stabilization of sensitivity. Furthermore, it is also effective to subject the developed image to full surface heating or full exposure for the purpose of improving image strength and printing durability. Usually, heating before development is preferably performed under a mild condition of 150 ° C. or less. If the temperature is too high, problems such as curing of unexposed portions may occur. Very strong conditions are used for heating after development. Usually, it is the range of 100-500 degreeC. If the temperature is low, sufficient image strengthening action cannot be obtained, and if it is too high, problems such as deterioration of the support and thermal decomposition of the image area may occur.

  EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In addition, unless otherwise indicated, in the polymer mentioned later, ratio of a repeating unit is molar ratio.

[Preparation of lithographic printing plate precursor (1)]
<Preparation of support (1)>
An aluminum plate (material 1050, tempered H16) having a thickness of 0.3 mm is immersed in a 10% by weight aqueous sodium hydroxide solution at 60 ° C. for 25 seconds, etched, washed with running water, and then neutralized and washed with a 20% by weight aqueous nitric acid solution. And then washed with water. This was subjected to an electrolytic surface roughening treatment in a 1% by mass nitric acid aqueous solution using an alternating waveform current of a sine wave at an anode time electricity of 300 coulomb / dm ² . Subsequently, after being immersed in a 1% by mass sodium hydroxide aqueous solution at 40 ° C. for 5 seconds, immersed in a 30% by mass sulfuric acid aqueous solution and desmutted at 60 ° C. for 40 seconds, the current density in a 20% by mass sulfuric acid aqueous solution was obtained. Anodization was performed for 2 minutes so that the thickness of the anodized film was 2.7 g / m ² under the condition of ² A / dm ² . Further, after being immersed in a 1% by mass polyvinyl phosphonic acid aqueous solution at 60 ° C. for 10 seconds, washed with hard water having a calcium ion concentration of 75 ppm at 20 ° C. and then with pure water for 4 seconds each, dried and hydrophilized for support. (1) was produced. The adhesion amount of calcium was 1.8 mg / m ² . When the surface roughness of the support was measured, it was 0.28 μm (Ra display according to JIS B0601).

<Formation of Image Recording Layer (1)>
An image recording layer coating solution (1) having the following composition was bar-coated on the support (1), followed by oven drying at 90 ° C. for 60 seconds, and an image recording layer (1) having a dry coating amount of 1.3 g / m ^2. Formed.

<Image recording layer coating solution (1)>
-The following binder polymer (1) (mass average molecular weight: 50,000) 0.34 g
・ The following polymerizable compound (1) 0.68 g
(PLEX6661-O, manufactured by Degussa Japan)
・ The following sensitizing dye (1) 0.06 g
・ The following polymerization initiator (1) 0.18 g
・ The following chain transfer agent (1) 0.02 g
・ 0.40 g of ε-phthalocyanine pigment dispersion
(Pigment: 15 parts by mass, dispersant (allyl methacrylate / methacrylic acid copolymer (mass average molecular weight: 60,000, copolymer molar ratio: 83/17)): 10 parts by mass,
(Cyclohexanone: 15 parts by mass)
・ Thermal polymerization inhibitor 0.01g
N-nitrosophenylhydroxylamine aluminum salt-The following fluorosurfactant (1) (mass average molecular weight: 10,000) 0.001 g
・ 3.5 g of 1-methoxy-2-propanol
・ Methyl ethyl ketone 8.0g

<Formation of protective layer (1)>
On the image recording layer (1), a protective layer coating solution (1) having the following composition was applied using a bar so that the dry coating amount was 1.5 g / m ^2, and then dried at 125 ° C. for 70 seconds. Thus, a protective layer (1) was formed to obtain a lithographic printing plate precursor (1).

<Protective layer coating solution (1)>
・ 0.6 g of the following mica dispersion (1)
・ Sulphonic acid-modified polyvinyl alcohol 0.8g
(Goselan CKS-50, manufactured by Nippon Synthetic Chemical Co., Ltd., degree of saponification:
99 mol%, average degree of polymerization: 300, degree of modification: about 0.4 mol%)
・ Poly (vinyl pyrrolidone / vinyl acetate (molar ratio: 1/1)) 0.001 g
(Mass average molecular weight: 70,000)
・ Surfactant (Emalex 710, manufactured by Nippon Emulsion Co., Ltd.) 0.002g
・ Water 13g

(Preparation of mica dispersion (1))
To 368 g of water, 32 g of synthetic mica (Somasif ME-100, manufactured by Corp Chemical Co., aspect ratio: 1000 or more) was added and dispersed using a homogenizer until the average particle size (laser scattering method) became 0.5 μm. A dispersion (1) was obtained.

[Preparation of lithographic printing plate precursor (2)]
<Preparation of support (2)>
An aluminum plate (material 1050, tempered H16) having a thickness of 0.3 mm is immersed in a 10% by weight aqueous sodium hydroxide solution at 60 ° C. for 25 seconds, etched, washed with running water, and then neutralized and washed with a 20% by weight aqueous nitric acid solution. And then washed with water. This was subjected to an electrolytic surface roughening treatment in a 1% by mass nitric acid aqueous solution using an alternating waveform current of a sine wave at an anode time electricity of 300 coulomb / dm ² . Subsequently, after being immersed in a 1% by mass sodium hydroxide aqueous solution at 40 ° C. for 5 seconds, immersed in a 30% by mass sulfuric acid aqueous solution and desmutted at 60 ° C. for 40 seconds, the current density in a 20% by mass sulfuric acid aqueous solution was obtained. Anodization was performed for 2 minutes so that the thickness of the anodized film was 2.7 g / m ² under the condition of ² A / dm ² . When the surface roughness of the aluminum plate thus treated was measured, it was 0.28 μm (Ra indication according to JIS B0601).

The following undercoat layer coating solution (1) was applied to the aluminum plate using a bar coater, and dried at 80 ° C. for 20 seconds to prepare a support (2). Subbing layer coating weight after drying was 12 mg / ^{m 2.}

<Undercoat layer coating solution (1)>
The following polymer (SP1) 0.87g
The following polymer (SP2) 0.73g
500.0 g of pure water
Methanol 500.0g

<Formation of image recording layer (2)>
An image recording layer coating liquid (2) having the following composition was bar-coated on the support (2), followed by oven drying at 125 ° C. for 34 seconds, and an image recording layer (2) having a dry coating amount of 1.4 g / m ^2. Formed.

<Image recording layer coating solution (2)>
-0.038g of the following infrared absorber (IR-1)
-0.061 g of the following polymerization initiator (S-1)
-0.094 g of the following polymerization initiator (I-1)
・ The chain transfer agent (1) 0.015 g
・ The following ethylenically unsaturated compound (M-1) 0.425 g
(A-BPE-4, Shin-Nakamura Chemical Co., Ltd.)
-0.311 g of the following binder polymer (B-1) (mass average molecular weight: 110,000)
-The following binder polymer (B-2) (mass average molecular weight: 100,000) 0.250 g
・ The following binder polymer (B-3) (mass average molecular weight: 120,000) 0.062 g
・ Polyoxyethylene-polyoxypropylene condensate 0.010 g
(Pluronic L44, manufactured by ADEKA Corporation)
・ 0.079g of the following additive (T-1)
-The following polymerization inhibitor (Q-1) 0.0012g
・ The following ethyl violet (EV-1) 0.021 g
-Fluorosurfactant (1) (mass average molecular weight: 10,000) 0.0081 g
・ Methyl ethyl ketone 5.886g
・ Methanol 2.733g
・ 1-methoxy-2-propanol 5.886 g

  In the following formulae, Me represents a methyl group.

<Formation of protective layer (2)>
On the image recording layer (1), the protective layer coating solution (1) having the above composition was applied using a bar so that the dry coating amount was 1.5 g / m ^2, and then dried at 125 ° C. for 70 seconds. Thus, a protective layer (1) was formed to obtain a lithographic printing plate precursor (2).

[Preparation of lithographic printing plate precursor (3)]

<Preparation of support (3)>
In order to remove rolling oil on the surface of an aluminum plate (material 1050, tempered H16) having a thickness of 0.3 mm, a degreasing treatment was performed at 50 ° C. for 30 seconds using a 10 mass% sodium aluminate aqueous solution, and then the bristle diameter The aluminum surface was grained using ^three 0.3 mm bundled nylon brushes and a pumice-water suspension (specific gravity 1.1 g / cm ³ ) having a median diameter of 25 μm and washed well with water. This plate was etched by being immersed in a 25 mass% aqueous sodium hydroxide solution at 45 ° C for 9 seconds, washed with water, further immersed in a 20 mass% nitric acid aqueous solution at 60 ° C for 20 seconds, and washed with water. The etching amount of the grained surface at this time was about 3 g / m ² .

Next, an electrochemical roughening treatment was performed continuously using an alternating voltage of 60 Hz. The electrolytic solution at this time was a 1% by mass nitric acid aqueous solution (containing 0.5% by mass of aluminum ions) and a liquid temperature of 50 ° C. The AC power source waveform is electrochemical roughening treatment using a trapezoidal rectangular wave alternating current with a time ratio TP of 0.8 msec until the current value reaches a peak from zero, a duty ratio of 1: 1, and a trapezoidal rectangular wave alternating current. Went. Ferrite was used for the auxiliary anode. The current density was 30 A / dm ² at the peak current value, and 5% of the current flowing from the power source was shunted to the auxiliary anode. The amount of electricity in nitric acid electrolysis was 175 C / dm ² when the aluminum plate was the anode. Then, water washing by spraying was performed.

Next, a 0.5% by mass hydrochloric acid aqueous solution (containing 0.5% by mass of aluminum ions) and an electrolytic solution having a liquid temperature of 50 ° C. and nitric acid electrolysis under the condition of an electric quantity of 50 C / dm ² when the aluminum plate is an anode. In the same manner as above, an electrochemical surface roughening treatment was performed, followed by washing with water by spraying. The plate was provided with a DC anodized film of 2.5 g / m ² at a current density of 15 A / dm ² using a 15 mass% sulfuric acid aqueous solution (containing 0.5 mass% of aluminum ions) as an electrolyte, then washed with water and dried. . Then, it processed at 20 degreeC for 10 second with 1 mass% of sodium silicate aqueous solution. The surface roughness of the aluminum plate thus treated was measured and found to be 0.54 μm (Ra indication according to JIS B0601).

The following undercoat layer coating solution (2) was applied to the aluminum plate using a bar coater and dried at 80 ° C. for 20 seconds to prepare a support (3). The coating amount of the undercoat layer after drying was 15 mg / m ² .

<Undercoat layer coating solution (2)>
The following polymer (SP3) 2.7 g
900.0g of pure water
Methanol 100.0g

<Formation of image recording layer (3)>
On the support (3), the binder polymer (1) (mass average molecular weight: 50,000) of the image recording layer coating liquid (1) having the above composition was added to the following binder polymer (2) (mass average molecular weight: 35,000). Then, the image recording layer coating solution (3) changed to the above was coated with a bar and then oven-dried at 90 ° C. for 60 seconds to form an image recording layer (3) having a dry coating amount of 1.3 g / m ² .

<Formation of protective layer (1)>
On the image recording layer (3), the protective layer coating solution (1) having the above composition was applied using a bar so that the dry coating amount was 1.5 g / m ^2, and then dried at 125 ° C. for 70 seconds. Thus, a protective layer (1) was formed to obtain a lithographic printing plate precursor (3).

[Preparation of lithographic printing plate precursor (4)]
<Preparation of support (4)>
An aluminum plate (material 1050, tempered H16) having a thickness of 0.24 mm was immersed in a 5% aqueous sodium hydroxide solution kept at 65 ° C., degreased for 1 minute, and then washed with water. The aluminum plate was neutralized by immersion in a 10% aqueous hydrochloric acid solution maintained at 25 ° C. for 1 minute, and then washed with water. Next, the aluminum plate was subjected to electrolytic surface roughening with an alternating current for 60 seconds under conditions of 25 ° C. and a current density of 100 A / dm ^{2 in} a 0.3 mass% hydrochloric acid aqueous solution, and then maintained at 60 ° C. A desmut treatment for 10 seconds was performed in a 5% aqueous sodium hydroxide solution. This aluminum plate was anodized in a 15% sulfuric acid aqueous solution at 25 ° C., a current density of 10 A / dm ² , and a voltage of 15 V for 1 minute, and further immersed in a 1% polyvinyl phosphonic acid aqueous solution at 60 ° C. for 10 seconds. After that, the substrate was washed with hard water having a calcium ion concentration of 75 ppm at 20 ° C. and then with pure water for 4 seconds each, dried and hydrophilized to prepare a support (4). The adhesion amount of calcium was 2.0 mg / m ² . When the surface roughness of the support was measured, it was 0.44 μm (Ra display according to JIS B0601).

<Formation of image recording layer (4)>
An image recording layer coating solution (4) having the following composition was bar-coated on the support, followed by oven drying at 90 ° C. for 60 seconds to form an image recording layer (4) having a dry coating amount of 1.3 g / m ^2. Formed.

Image recording layer coating solution (4)
-Binder polymer (1) (mass average molecular weight: 50,000) 0.04 g
-The following binder polymer (3) (mass average molecular weight: 80,000) 0.30 g
-0.68 g of the above polymerizable compound (1)
・ The following sensitizing dye (2) 0.03 g
・ The following sensitizing dye (3) 0.015 g
・ The following sensitizing dye (4) 0.015 g
・ The above polymerization initiator (1) 0.13 g
・ Chain transfer agent: Mercaptobenzothiazole 0.01g
・ 0.40 g of ε-phthalocyanine pigment dispersion
(Pigment: 15 parts by mass, dispersant (allyl methacrylate / methacrylic acid copolymer (mass average molecular weight: 60,000, copolymer molar ratio: 83/17)): 10 parts by mass, cyclohexanone: 15 parts by mass)
・ Thermal polymerization inhibitor 0.01g
N-nitrosophenylhydroxylamine aluminum salt-Fluorosurfactant (1) (mass average molecular weight: 10,000) 0.001 g
・ 3.5 g of 1-methoxy-2-propanol
・ Methyl ethyl ketone 8.0g
・ N, N dimethylaminopropyl methacrylamide 0.015g

<Formation of protective layer (2)>
On the image recording layer (4), a protective layer coating solution (2) having the following composition was applied using a bar so that the dry coating amount was 1.2 g / m ^2, and then 125 ° C., 70 seconds. Was dried to form a protective layer (2) to obtain a lithographic printing plate precursor (4).

<Protective layer coating solution (2)>
・ PVA-205 0.658g
(Partially hydrolyzed polyvinyl alcohol, manufactured by Kuraray Co., Ltd., degree of saponification = 86.5-89.5 mol%, viscosity = 4.6-5.4 mPa · s (in 20 ° C., 4% by mass aqueous solution))
・ PVA-105 0.142g
(Completely hydrolyzed polyvinyl alcohol, manufactured by Kuraray Co., Ltd., degree of saponification = 98.0-99.0 mol%, viscosity = 5.2-6.0 mPa · s (in 20 ° C., 4 mass% aqueous solution))
・ Poly (vinyl pyrrolidone / vinyl acetate (molar ratio 1/1)) (mass average molecular weight 70,000)
0.001g
・ Surfactant (trade name “Emalex 710”, manufactured by Nippon Emulsion Co., Ltd.)
0.002g
・ Water 13g

<Developer A>
・ The following surfactant-1 (manufactured by Kawaken Fine Chemical Co., Ltd .: Softazoline LPB-R)
15g
・ The following surfactant-2 (Kawaken Fine Chemical Co., Ltd .: Softazolin LAO)
4g
・ Chelating agent Ethylenediamine succinic acid trisodium (manufactured by InnoSpec specialty chemicals: ENVIOMET C140) 0.68 g
・ 2-Bromo-2-nitropropane-1,3diol 0.025g
・ 2-Methyl-4-isothiazolin-3-one 0.025 g
・ Silicone-based antifoaming agent (GE Toshiba Silicones Co., Ltd .: TSA739) 0.15 g
・ Sodium gluconate 1.5g
・ Sodium carbonate 1.06g
・ Sodium bicarbonate 0.52g
・ Water 77.04g
・ Lipase (Novozymes Japan: NS44126) 0.3g
* The pH was 9.8.

<Developer B>
Surfactant-3 Polyoxyethylene naphthyl ether (Nippon Emulsifier Co., Ltd .: New Coal B-13)
3g
-Chelating agent Ethylenediamine succinic acid trisodium (InnoSpec special chemicals: Octaquest E30)
0.68g
・ 2-Bromo-2-nitropropane-1,3diol 0.025g
・ 2-Methyl-4-isothiazolin-3-one 0.025g
・ Silicone-based antifoaming agent (GE Toshiba Silicones Co., Ltd .: TSA739) 0.15 g
・ Sodium gluconate 1.5g
・ Sodium carbonate 1.06g
・ Sodium bicarbonate 0.52g
・ Water 77.04g
・ Lipase (Novozymes Japan: NS44126) 0.3g
* The pH was 9.8.

<Developer C>
Nonionic surfactant (BASF: Pluronic PE9400 (ethylene oxide / propylene oxide block copolymer)) 2.5 g
Nonionic surfactant (manufactured by CLARIANT: Emarzogen TS160 (2,4,6-tris- (1-phenylethyl) -phenol-ethylate) 2.5 g
・ 1.0 g of 1-phenoxy-2-propanol
・ Triethanolamine 0.6g
・ Phosphoric acid (85%) 0.3g
・ Sodium gluconate 1.0g
・ Trisodium citrate 0.5g
・ Ethylenediaminetetraacetate tetrasodium salt 0.05g
Polystyrene sulfonic acid (trade name “Versa TL77 (30 mass% solution)”, manufactured by Alco chemical) 1.0 g
・ Water 90.55g
* Sodium hydroxide and phosphoric acid were further added to the treatment liquid having the above composition to adjust the pH to 6.9.

<Developer D>
Hydroxypropyl etherified starch (Nippon Chemical Co., Ltd., Penon JE66) 8.71 g
Gum arabic (manufactured by CNI, litho gum # 60030) 1.58 g
Phosphate esterified starch (Nippon Chemical Co., Ltd., Petrocoat PN11) 0.79g
0.10 g of primary ammonium phosphate
0.17 g of lauryl diphenyl ether disulfonic acid 2Na salt (manufactured by Sanyo Kasei, Eleminol MON2)
Dioctylsulfosuccinic acid 2Na salt (manufactured by NOF Corporation, Rapisol B80) 0.10 g
Benzyl alcohol 0.87g
Ethylene glycol 0.79g
EDTA · 4Na (Nippon Kyrest, Kyrest 400) 0.08g
0.014 g of silicone-based antifoaming agent (GE Toshiba Silicones Co., Ltd .: TSA739)
Benzisothiazolone (manufactured by Zeneca, Proxel GXL) 0.012 g
86.78g water
* Sodium hydroxide and phosphoric acid were further added to the treatment liquid having the above composition to adjust the pH to 4.5.

<Image exposure>
The lithographic printing plate precursors (1), (3), (4) are disclosed in FUJIFILM Electronic Imaging Ltd. Image exposure was performed using a Violet semiconductor laser plate setter Vx9600 manufactured by InGaN-based semiconductor laser 405 nm ± 10 nm emission / output 30 mW. Image exposure was carried out using a FM film (TAFFET A20) manufactured by Fuji Film Co., Ltd. with a resolution of 2438 dpi and a 50% flat screen with a plate exposure of 0.05 mJ / cm ² . The lithographic printing plate precursor (2) is a 50% flat screen image under conditions of 9 W output, outer drum rotation speed 210 rpm, resolution 2, 400 dpi using a Trendsetter 3244VX (equipped with water-cooled 40 W infrared semiconductor laser (830 nm)) manufactured by Creo. Exposure was performed.

[Examples 1 and 2 and Comparative Examples 1 and 2]

  In Examples 1 and 2, the lithographic printing plate precursor (1) was image-exposed as described above, and then the lithographic printing plate precursor was developed using the same developing apparatus as shown in FIG.

  In Comparative Examples 1 and 2, the lithographic printing plate precursor (1) was image-exposed as described above, and then the lithographic printing plate precursor was developed using a developing device not equipped with a replenishing unit and a liquid feeding device. The developing devices of Comparative Examples 1 and 2 have the same configuration as that of Examples 1 and 2 unless otherwise described below, except for the replenishment unit and the liquid feeding device. Further, the description of the configuration of the developing device will refer to the configuration of FIG. 2 as appropriate.

  The preheating unit 50 has a heating unit, and the heating conditions were 100 ° C. and 10 seconds.

  The liquid temperature of the developer in the example and the comparative example is maintained at 25 ° C., and the lithographic printing plate precursor 10 is carried in from the conveying roller pair 22 on the upstream side of the tank 20 of the first processing unit, and the downstream side of the tank 20 The conveyance speed was set so that the transit time from the pair of conveyance rollers 24 to 20 seconds was 20 seconds.

  The rubbing member 26 is a member that rotates about a rotation axis, and the rotation direction is set to drive in the forward direction with respect to the transport direction. The outer diameter of the rubbing member 26 was φ50 mm.

  The planographic printing plate precursor 10 carried out from the tank 20 of the first processing unit 2 passed through the drying unit 52 and was dried. The drying temperature (plate surface) was about 55 ° C. (Note that the plate surface temperature is preferably set in the range of 50 to 60 ° C., but the set temperature is not limited to this range because it should be set in accordance with the treatment liquid. .)

For Examples 1 and 2 and Comparative Examples 1 and 2, the lithographic printing plate precursor was subjected to 500 m ² plate passing, and the stain on the lithographic printing plate precursor after development and the contamination status in the developing device were evaluated. The results are shown in Table 1.

  In the evaluation of stains on the lithographic printing plate precursor, 10 lithographic printing plate precursors were sampled and the number of debris adhering to the lithographic printing plate precursor at this time was evaluated.

  The state of contamination of the developing device was evaluated from the viewpoint of visual observation of stains when the developer and washing water were drained from each of the tanks 20, 30, and 40 and whether they could be easily removed. In the following description, the tanks 20, 30, and 40 are also referred to as a first bath, a second bath, and a third bath for simplification.

  In Example 1, in the developing device 1 having the configuration shown in FIG. 2, the developing solution A is stored in the tank 20, the washing water is stored in the second bath, and the developing solution A is stored in the third bath.

  In the second embodiment, the developing device 1 having the same configuration as that of the first embodiment is used, and the concentrated solution of the developer A is used as the developer stored in the tank 40.

In Comparative Example 1, the developing device 1 having the same configuration as in Examples 1 and 2 is used, and the developer A is stored in the tank 20, the washing water is stored in the tank 30, and the developer D is stored in the tank 40. Liquid feeding from the tank 40 to the tank 20 is not performed.
In Comparative Example 2, the developing device 1 having the same configuration as in Examples 1 and 2 is used, and the developer A is stored in the tank 20, the flush water is stored in the tank 30, and the developer A is stored in the tank 40. Liquid feeding from the tank 40 to the tank 20 is not performed.

(Evaluation criteria)
As an evaluation standard for dirt on the planographic printing plate precursor (the number of debris adhering to the plate), 10 samples were sampled and the number of debris per unit area at this time was evaluated. ˜5 / m ² was “Δ”, and 6 or more / m ² was “×”.

  The evaluation criteria for the contamination of the developing device are “◎” when there is almost no dirt at the liquid draining stage and even a slight dirt can be easily dropped with water. The condition where the water drops falls is marked with “○”, and it is impossible to completely remove dirt with water alone. The state where dirt can be removed by rubbing is indicated by “Δ”, and the state where dirt is not removed even by rubbing is indicated by “x”.

(Processable amount)
The prepared lithographic printing plate is attached to a Lislon printing machine manufactured by Komori Corporation, and “Barius G” ink from Dainippon Ink and Chemicals is used as ink, and Fujifilm is used as dampening water. Using “IF-102” diluted with water to a concentration of 4% by volume, printing was performed at a printing speed of 6000 sheets per hour, and the smudge of the non-image area was evaluated on the 1000th printed matter. The processing amount (processing life) of the lithographic printing plate precursor until ink stains occurred in the non-image area was evaluated as the processing amount.

According to the evaluation results, in Examples 1 and 2, there was no contamination in the developing device even during long-term use, and no contamination due to adhesion of residue etc. occurred on the planographic printing plate precursor. In Examples 1 and 2, the developer is replenished to the third bath in anticipation of replenishment of the first bath by the replenishing unit, and the developer is fed from the first bath to the third bath using a liquid feeder. Therefore, the degree of contamination is reduced much more than in Comparative Example 1. For this reason, in Examples 1 and 2, the inside of the third bath is kept clean, and no stain is generated on the lithographic printing plate precursor.

In Comparative Example 1, the third bath, which is the final bath, is gradually contaminated by repeated development processing, and the lithographic printing plate precursor is also contaminated with debris at a rate of about 2 pieces / m ^2. I understood. In Comparative Example 1, the first bath is contaminated, the contaminated processing liquid is brought into the second bath, and the second bath is contaminated. Further, the contaminated water in the second bath is brought into the third bath, and the treatment liquid D in the third bath is contaminated. For this reason, the third bath is contaminated, and the lithographic printing plate precursor is confirmed to be contaminated by debris of the image recording layer.

  As described above, it is considered that it is important to keep the final bath in a fresh state as in Examples 1 and 2 in consideration of the contamination status in the developing device and the occurrence of contamination on the planographic printing plate precursor. .

  Further, the amount of liquid sent from the third bath to the first bath is not always sent, but at the time of feeding, 100 cc is fed per minute, and the replenishment amount to the third bath It is set slightly less than 120cc / min.

[Examples 3a to 3d]
In Examples 3a to 3d, in the developing device used in Example 1, the temperature of the developer to be fed and the temperature when the amount of the developer to be fed from the third bath to the first bath is changed. Variation (temperature difference). The evaluation results are shown in Table 2.

  The evaluation criteria for temperature stability are “◯” when the temperature difference is less than 0.5 ° C., “◯ △” when the temperature difference is 0.5 ° C. to less than 1 ° C., and 1 ° C. temperature difference. When the temperature difference was 2 ° C. or more, “X” was assigned.

  Table 2 shows the results when the amount of liquid fed from the third bath to the first bath was changed in the embodiment of Example 1. For the evaluation of temperature instability, the temperature difference between the location 5 cm away from the pipe recovery port from the third bath to the first bath and the center of the tank was taken. It was found that the temperature non-uniformity becomes large at a liquid feeding amount exceeding 1 L / min.

[Examples 4 to 8]
In Examples 4 to 8, using the developing device of Example 1, the stains on the planographic printing plate precursor and the contamination of the third bath when the types of the developer stored in the first bath and the third bath are changed are used. It has been evaluated. Table 3 shows the evaluation results.

  Good results were obtained for any of Examples 4 to 8.

[Example 10, Reference Example 1]
Next, based on Example 10 and Reference Example 1, the effect of the developing device of the present invention is verified.

  Example 10 has basically the same configuration as the developing device described in FIG. 2, and uses a developer stored in each of the first to third baths.

  In Reference Example 1, a developing device having the same configuration as that of Example 10 was used except that the replenishment unit and the liquid feeding device were not provided. In Reference Example 1, the developer stored in the second bath is overflowed and fed to the first bath without passing through a pipe.

  The evaluation criteria for the stain on the planographic printing plate precursor and the third bath stain in the developing device are the same as those described above. The evaluation criteria for the stability of the treatment liquid in one bath were “◯” when the liquid level was controlled and “Δ” when the problem of liquid level drop occurred.

  According to the evaluation results, Example 10 is good with almost no plate stains and three bath stains in the apparatus. In Example 10, the developer is fed from the third bath through a pipe, and the amount of developer supplied to the first bath can be accurately controlled. The treatment liquid can be fed from the third bath to the first bath with high accuracy.

In Reference Example 1, since the overflow amount of the rear bath is poured into the first bath without using piping, the supply amount is not stable. Even in this experiment, the treatment liquid adhered to the overflow channel provided between the tanks, and the liquid feeding became insufficient, resulting in a problem that the liquid level of the first bath was lowered. For this reason, the development time in the first bath was shortened, and development failure occurred when the processing amount exceeded 1300 m ² .

The present specification discloses the following contents.
(1) A lithographic printing plate precursor developing device for carrying out development by transporting a lithographic printing plate precursor having a support and an exposed image recording layer supported on the support,
A first developing section which has a first tank and develops the image recording layer by immersing the transported lithographic printing plate precursor in a developer stored in the first tank;
A second developing section, which is disposed downstream of the first developing section in the transport direction of the lithographic printing plate precursor and has a second tank for storing a developer;
A replenisher for replenishing the second tank with fresh developer;
A liquid feeding device for feeding the developer stored in the second tank from the second tank to the first tank, and
The liquid feeding device is a lithographic printing plate precursor developing device that feeds the developer stored in the second tank to the first tank.
(2) A lithographic printing plate precursor developing device according to (1),
A rinsing section for rinsing the lithographic printing plate precursor conveyed from the first developing section;
The water washing section is downstream in the transport direction of the lithographic printing plate precursor with respect to the first development section, and upstream in the transport direction of the lithographic printing plate precursor with respect to the second development section. Development equipment for lithographic printing plate precursors.
(3) The lithographic printing plate precursor development apparatus according to (1) or (2),
The lithographic printing plate precursor developing device, wherein the liquid feeding device has a closed path, and the developer is fed to the first tank through the closed path.
(4) A method for developing a lithographic printing plate precursor using a developing device for transporting and developing a lithographic printing plate precursor having a support and an exposed image recording layer supported on the support. ,
The developing device has a first tank, a first developing unit that develops the image recording layer by immersing the transported lithographic printing plate precursor in a developer stored in the first tank;
A second developing unit that is disposed downstream of the first developing unit in the transport direction of the lithographic printing plate precursor and has a second tank for storing a developer, and
Developing the image recording layer by immersing the planographic printing plate in a developer stored in the first tank;
Replenishing the second tank with a fresh developer disposed downstream of the first tank in the transport direction of the planographic printing plate;
And a step of feeding the developer stored in the second tank to the first tank using a liquid feeding device.
(5) The method for developing a lithographic printing plate as described in (4),
A method for developing a lithographic printing plate comprising the steps of washing the lithographic printing plate after being transported from the first tank and before being transported to the second tank.
(6) The lithographic printing plate development method according to (4) or (5),
The image recording layer includes (A) a polymerization initiator, (B) a polymerizable compound, (C) a sensitizing dye, and (D) a binder polymer.
A protective layer is formed on the image recording layer,
The developer contains at least one of a surfactant and a hydrophilic polymer compound, and has a pH of 2.0 or more and less than 10.0.
A lithographic printing plate developing method comprising the step of removing at least a part of the protective layer and the image recording layer of the non-exposed portion in the first tank.
(7) The lithographic printing plate development method according to (6),
A method for developing a lithographic printing plate, wherein the surfactant is at least one of a zwitterionic surfactant and a nonionic surfactant.
(8) The method for developing a lithographic printing plate according to (7),
The zwitterionic surfactant is at least one of the zwitterionic surfactants represented by the following general formula (1) or (2), and the nonionic surfactant is represented by the following general formula (3): The method for developing a lithographic printing plate according to claim 10, which is at least one of the nonionic aromatic ether surfactants represented.

式（１）及び（２）中、Ｒ^１及びＲ^１１は、各々独立に、炭素数８〜２０のアルキル基又は総炭素数８〜２０の連結基を有するアルキル基を表し、Ｒ^２、Ｒ^３、Ｒ^１２及びＲ^１３は、各々独立に、水素原子、アルキル基又はエチレンオキサイド基を含有する基を表し、Ｒ^４及びＲ^１４は、各々独立に、単結合又はアルキレン基を表し、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４のうち２つの基は互いに結合して環構造を形成してもよく、Ｒ^１１、Ｒ^１２、Ｒ^１３及びＲ^１４のうち２つの基は互いに結合して環構造を形成してもよい。
Ｘ−Ｙ−Ｏ−（Ａ）ｎ−（Ｂ）ｍ−Ｈ （３）
式（３）中、Ｘは芳香族基を表し、Ｙは単結合又は炭素数１〜１０のアルキレン基を表し、Ａ及びＢは互いに異なる基であって、−ＣＨ_２ＣＨ_２Ｏ−又は−ＣＨ_２ＣＨ（ＣＨ_３）Ｏ−を表し、ｎ及びｍは各々０〜１００の整数を表す。但しｎ及びｍの和は２以上である。
（９）（４）〜（８）のうちいずれか１項に記載の平版印刷版の現像方法であって、
前記現像液が、更に、ｐＨ緩衝剤を含む平版印刷版の作製方法。
（１０）（９）に記載の平版印刷版の現像方法であって、
前記ｐＨ緩衝剤が、炭酸イオン及び炭酸水素イオンである平版印刷版の現像方法。
（１１）（９）に記載の平版印刷版の現像方法であって、
前記ｐＨ緩衝剤が、水溶性のアミン化合物及びそのアミン化合物のイオンである平版印刷版の現像方法。
（１２）（４）〜（１１）のいずれか１つに記載の平版印刷版の現像方法であって、
前記重合性化合物が、ウレタン結合又はウレア結合を有する平版印刷版の現像方法。
（１３）（６）〜（１２）のいずれか１つに記載の平版印刷版の現像方法であって、
前記バインダーポリマーの質量に対する前記重合性化合物の質量の比が、１．２５〜４．５である平版印刷版の現像方法。

In the formulas (1) and (2), R ¹ and R ¹¹ each independently represents an alkyl group having 8 to 20 carbon atoms or a linking group having 8 to 20 carbon atoms in total, R ² , R 11 ³ , R ¹² and R ¹³ each independently represents a group containing a hydrogen atom, an alkyl group or an ethylene oxide group, R ⁴ and R ¹⁴ each independently represents a single bond or an alkylene group, and R ¹ , R ² , R ³ and R ⁴ may be bonded to each other to form a ring structure, and two groups of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ may be bonded to each other to form a ring. A structure may be formed.
X-Y-O- (A) n- (B) m-H (3)
In formula (3), X represents an aromatic group, Y represents a single bond or an alkylene group having 1 to 10 carbon atoms, A and B are groups different from each other, and represent —CH ₂ CH ₂ O— or — CH ₂ CH (CH ₃ ) O— is represented, and n and m each represents an integer of 0 to 100. However, the sum of n and m is 2 or more.
(9) The method for developing a lithographic printing plate according to any one of (4) to (8),
A method for preparing a lithographic printing plate, wherein the developer further contains a pH buffer.
(10) The method for developing a lithographic printing plate according to (9),
A development method of a lithographic printing plate, wherein the pH buffer is a carbonate ion and a hydrogen carbonate ion.
(11) The method for developing a lithographic printing plate according to (9),
A method for developing a lithographic printing plate, wherein the pH buffer is a water-soluble amine compound and ions of the amine compound.
(12) The method for developing a lithographic printing plate according to any one of (4) to (11),
A method for developing a lithographic printing plate, wherein the polymerizable compound has a urethane bond or a urea bond.
(13) The method for developing a lithographic printing plate according to any one of (6) to (12),
A method for developing a lithographic printing plate, wherein a ratio of a mass of the polymerizable compound to a mass of the binder polymer is 1.25 to 4.5.

DESCRIPTION OF SYMBOLS 1 Planographic printing plate processing apparatus 2 1st processing part 3 2nd processing part 4 3rd processing part 20, 30, 40 Tank 60 Replenishment part 80 Pipe 84 Tank 86 Pump

Claims (13)

A lithographic printing plate precursor developing device for carrying out development by transporting a lithographic printing plate precursor having a support and an exposed image recording layer supported on the support,
A first developing section which has a first tank and develops the image recording layer by immersing the transported lithographic printing plate precursor in a developer stored in the first tank;
A second developing section, which is disposed downstream of the first developing section in the transport direction of the lithographic printing plate precursor and has a second tank for storing a developer;
A replenisher for replenishing the second tank with fresh developer;
A liquid feeding device for feeding the developer stored in the second tank from the second tank to the first tank, and
The liquid feeding device is a lithographic printing plate precursor developing device that feeds the developer stored in the second tank to the first tank. A lithographic printing plate precursor developing device according to claim 1,
A rinsing section for rinsing the lithographic printing plate precursor conveyed from the first developing section;
The water washing section is downstream in the transport direction of the lithographic printing plate precursor with respect to the first development section, and upstream in the transport direction of the lithographic printing plate precursor with respect to the second development section. Development equipment for lithographic printing plate precursors. A developing device for a lithographic printing plate precursor as claimed in claim 1 or 2,
The lithographic printing plate precursor developing device, wherein the liquid feeding device has a closed path, and the developer is fed to the first tank through the closed path. A method for developing a lithographic printing plate precursor using a developing device that transports and develops a lithographic printing plate precursor having a support and an exposed image recording layer supported on the support,
The developing device has a first tank, a first developing unit that develops the image recording layer by immersing the transported lithographic printing plate precursor in a developer stored in the first tank;
A second developing unit that is disposed downstream of the first developing unit in the transport direction of the lithographic printing plate precursor and has a second tank for storing a developer, and
Developing the image recording layer by immersing the planographic printing plate in a developer stored in the first tank;
Replenishing the second tank with a fresh developer disposed downstream of the first tank in the transport direction of the planographic printing plate;
And a step of feeding the developer stored in the second tank to the first tank using a liquid feeding device. A method for developing a lithographic printing plate according to claim 4,
A method for developing a lithographic printing plate comprising the steps of washing the lithographic printing plate after being transported from the first tank and before being transported to the second tank. A lithographic printing plate development method according to claim 4 or 5,
The image recording layer includes (A) a polymerization initiator, (B) a polymerizable compound, (C) a sensitizing dye, and (D) a binder polymer.
A protective layer is formed on the image recording layer,
The developer contains at least one of a surfactant and a hydrophilic polymer compound, and has a pH of 2.0 or more and less than 10.0.
A lithographic printing plate developing method comprising the step of removing at least a part of the protective layer and the image recording layer of the non-exposed portion in the first tank. A lithographic printing plate developing method according to claim 6,
A method for developing a lithographic printing plate, wherein the surfactant is at least one of a zwitterionic surfactant and a nonionic surfactant. A lithographic printing plate development method according to claim 7,
The zwitterionic surfactant is at least one of the zwitterionic surfactants represented by the following general formula (1) or (2), and the nonionic surfactant is represented by the following general formula (3): The method for developing a lithographic printing plate according to claim 10, which is at least one of the nonionic aromatic ether surfactants represented.

In the formulas (1) and (2), R ¹ and R ¹¹ each independently represents an alkyl group having 8 to 20 carbon atoms or a linking group having 8 to 20 carbon atoms in total, R ² , R 11 ³ , R ¹² and R ¹³ each independently represents a group containing a hydrogen atom, an alkyl group or an ethylene oxide group, R ⁴ and R ¹⁴ each independently represents a single bond or an alkylene group, and R ¹ , R ² , R ³ and R ⁴ may be bonded to each other to form a ring structure, and two groups of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ may be bonded to each other to form a ring. A structure may be formed.
X-Y-O- (A) n- (B) m-H (3)
In formula (3), X represents an aromatic group, Y represents a single bond or an alkylene group having 1 to 10 carbon atoms, A and B are groups different from each other, and represent —CH ₂ CH ₂ O— or — CH ₂ CH (CH ₃ ) O— is represented, and n and m each represents an integer of 0 to 100. However, the sum of n and m is 2 or more. A lithographic printing plate development method according to any one of claims 4 to 8,
A method for preparing a lithographic printing plate, wherein the developer further contains a pH buffer. A method for developing a lithographic printing plate according to claim 9,
A development method of a lithographic printing plate, wherein the pH buffer is a carbonate ion and a hydrogen carbonate ion. A method for developing a lithographic printing plate according to claim 9,
A method for developing a lithographic printing plate, wherein the pH buffer is a water-soluble amine compound and ions of the amine compound. A lithographic printing plate development method according to any one of claims 4 to 11, comprising:
A method for developing a lithographic printing plate, wherein the polymerizable compound has a urethane bond or a urea bond. A method for developing a lithographic printing plate according to any one of claims 6 to 12,
A method for developing a lithographic printing plate, wherein a ratio of a mass of the polymerizable compound to a mass of the binder polymer is 1.25 to 4.5.

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