JP2002113964A - Original plate for lithographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an original plate for a lithographic printing plate with such advantages that the adhesion between the plate and a support is excellent, the diffusion of heat to the aluminum support can be inhibited, an image can be formed by emitting a low-energy laser beam and a smear-free printed matter can be obtained even under severe printing conditions. SOLUTION: This original plate for the lithographic printing plate comprises a hydrophilic layer which is bonded with a substrate through covalent bonding and contains a polymer compound with a hydrophilic group and a recording group which contains a polymer compound with at least either of a carboxylic acid group or a carboxylate group selected from the group consisting of the described groups which cause decarboxylation by heat, laminated on the hydrophilic group, all of the layers being formed on the substrate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel lithographic printing plate precursor, and more particularly to a lithographic printing plate precursor which does not require an alkali developing treatment and has excellent sensitivity and stain resistance. The present invention relates to a lithographic printing plate precursor capable of performing scanning exposure of an image with a laser beam and directly making a plate.

[0002]

2. Description of the Related Art Conventionally, as a method of making a printing plate directly from digitized image data without passing through a lithographic film, an electrophotographic method or a method of writing with a relatively small output laser emitting blue or green light can be used. A method using a high-sensitivity photopolymer, a method using a silver salt or a composite system of a silver salt and another system, a method of generating an acid by heat mode laser exposure and obtaining a thermosetting image by post-heating using the acid as a catalyst, etc. It has been known.

Although these methods are extremely useful in streamlining the printing process, they are not always satisfactory at present. For example, in the case of using the electrophotographic method, an image forming process such as charging, exposure, and development is complicated, and the apparatus is complicated and large. Further, in the case of using the photopolymer, since a printing plate having high sensitivity is used, it is difficult to handle in a bright room. The method using a silver salt has disadvantages such as complicated processing and silver contained in the processing waste liquid. Also requires post-heating and subsequent development processing, which complicates the processing.

[0004] Further, in the production of these printing plates, after the exposure process, a wet development process for removing the recording layer provided on the surface of the support in an image-like manner or a printing plate subjected to the development process is used. A post-treatment step of washing with water, or treating with a rinse solution containing a surfactant, gum arabic, or a desensitizing solution containing a starch derivative is included. On the other hand, in the plate making and printing industries in recent years, plate making operations have been rationalized, and there has been a demand for a printing plate precursor that can be used for printing directly after exposure without the need for such a complicated wet development process.

As a printing plate which does not require a developing step, WO99 / 3
An organic polymer layer provided with a cross-linked hydrophilic layer on a substrate and comprising one or more polymers and a photothermal conversion dye capable of absorbing laser radiation as described in 7481, and absorptive light absorption There is a laser-recordable positive ablation printing original plate provided with an ink receptive surface layer consisting of: By using this printing original plate, it was possible to obtain a printing plate without the intended development processing, but there was a problem that stains gradually occurred as printing was performed. In addition, there was a problem that adhesion between the hydrophilic layer and the ink receiving layer was poor and printing durability was low.

Japanese Patent Application Laid-Open No. 2000-122272 discloses a heat-sensitive lithographic printing plate having a layer containing a hydrophilic polymer compound which can be unprocessed and changes in hydrophobicity by heat. The exposed portion changed to hydrophobic, and the polymer in the unexposed portion remained hydrophilic, so that the polymer was developed with dampening water on a printing press, so that it did not require any particular development processing. . However, since aluminum having high thermal conductivity was used as the substrate, heat generated by exposure and the action of the photothermal conversion agent was diffused into the aluminum substrate, and heat near the substrate surface was hardly increased. Therefore, the thermal reaction of the polymer in the photosensitive layer does not sufficiently proceed near the substrate and does not change to hydrophobicity. Therefore, the sensitivity is low, and it is necessary to increase the laser exposure in order to completely form an image portion.

[0007]

That is, these conventional techniques cannot provide a photosensitive material which is satisfactory in terms of sensitivity, stain resistance and printing durability, and the sensitivity of the image forming layer is higher from a practical viewpoint. Even under more severe printing conditions, there has been a demand for a lithographic printing plate precursor capable of obtaining a printed matter in which the image forming layer does not peel off from the support and is free from stains. Therefore, an object of the present invention is to solve the above-described problems of the conventional lithographic printing plate precursor, to have excellent adhesion to a support, and to suppress the diffusion of heat to an aluminum support, thereby achieving a lower It is an object of the present invention to provide a lithographic printing plate precursor capable of forming an image by laser irradiation with energy and obtaining a printed matter free of stain even under severe printing conditions.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies in order to achieve the above object, and as a result, for example, applied and dried a liquid composition containing a compound having an unsaturated group on an aluminum support. A substrate having an unsaturated group retained on the surface of the support is prepared, and the substrate is used. The substrate contains a polymer compound having a lower thermal conductivity than aluminum and having a photopolymerizable group. It is possible to provide a hydrophilic layer (heat insulating layer) in which polymer chains are chemically bonded to the substrate by irradiating ultraviolet rays or the like, and a carboxylic acid group and a carboxylic acid group that cause decarboxylation by heat on the hydrophilic layer. By providing a recording layer containing a polymer compound having at least any one group selected from the group consisting of acid bases, a lithographic printing plate having high sensitivity and excellent printing durability which does not cause stain even under severe printing conditions. It found that the printing plate precursor is obtained and have completed the present invention.

That is, the present invention is as follows. (1) On a substrate, a hydrophilic layer containing a polymer compound having a hydrophilic group which is bonded to the substrate via a covalent bond, and a carboxylic acid group and a carboxylic acid which cause decarboxylation on the hydrophilic layer by heat A lithographic printing plate precursor comprising: a recording layer containing a polymer compound having at least one group selected from the group consisting of acid bases. (2) The polymer compound causing decarboxylation by heat is at least one selected from the group represented by the following general formulas (1) and (2).
The lithographic printing plate precursor described in.

[0010]

Embedded image

(Wherein X is selected from the group consisting of elements of Groups 4 to 6, oxides, sulfides, selenides and tellurides, P represents a polymer main chain, and -L- Represents a divalent linking group, R ¹ and R ² each represent a monovalent group which may be the same or different, M represents an alkali metal,
Represents any one selected from the group consisting of alkaline earth metals and onium. )

As described above, the present inventors form a substrate having an unsaturated group on the surface of a support, and form a layer containing a polymer compound having an unsaturated group and a hydrophilic group on the substrate. After coating, a crosslinked hydrophilic layer having low thermal conductivity chemically bonded to the surface of the substrate by UV exposure (ultraviolet irradiation) or the like is provided, and on the crosslinked hydrophilic layer, a carboxylic acid group and a carboxylic acid which cause decarboxylation by heat are provided. By preparing a lithographic printing plate precursor having a recording layer containing a polymer having at least any group selected from the group consisting of bases, preferably a polymer selected from the group consisting of carboxylic acid groups having good developability, The diffusion of heat due to infrared laser exposure of the recording layer can be suppressed, and the solubility of the polymer compound in the recording layer in water can be completely converted. But sufficient image formation is performed, i.e. the effect of high sensitivity is obtained. In addition, since the hydrophilic layer is chemically bonded to the substrate surface, even if it swells, the adhesion to the substrate body does not deteriorate, and the printing durability is good even under severe printing conditions for a large number of sheets. A printed matter free of the occurrence of the above is obtained. Further, as a technique for the hydrophilic layer to exhibit hydrophilicity, a polymer compound having a radical polymerizable group in a side chain thereof may be prepared by copolymerizing a hydrophilic monomer or a polymer with a monomer having an ethylene addition polymerizable unsaturated group. The problem was solved by using a hydrophilic polymer compound which is Further, it is possible to provide a lithographic printing plate precursor which does not require plate making by a simple water developing treatment operation or which can be directly mounted on a printing machine for plate making without the need for developing treatment.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The lithographic printing plate precursor according to the present invention will be described in detail below. (Method for bonding substrate and hydrophilic layer) As a method for directly chemically bonding a functional group on the substrate surface and a polymer side chain functional group in the hydrophilic layer, which is a feature of the lithographic printing plate precursor of the present invention, with light, A method was used in which a functional group was introduced on the substrate surface, a functional group capable of binding with the functional group by light was introduced into the hydrophilic polymer side chain, and the functional group was bound by light. As a method for optically coupling the functional groups, photoradical polymerization, photodimerization reaction, diazo coupling reaction, and the like can be used. Specifically, the following functional groups can be considered. Photopolymerization by introducing unsaturated groups into the substrate surface and hydrophilic polymer side chains, photocrosslinking by introducing photodimerization groups such as cinnamylidene groups, and introduction of nucleophilic groups such as hydroxyl groups onto the substrate surface Method of diazo coupling with diazonium salt introduced into polymer side chain, generation of photo radicals such as triazine skeleton having unsaturated group introduced on substrate surface and trihalomethyl group introduced into hydrophilic polymer side chain as substituents Although a method of photopolymerization using a group is conceivable, a method of using an unsaturated group on the substrate surface and the hydrophilic polymer side chain is most preferable from the viewpoint of production suitability.

After the hydrophilic layer of the lithographic printing plate precursor according to the present invention is applied and formed on the substrate, the entire surface thereof is subjected to a photopolymerization reaction by ultraviolet irradiation or the like, as described above, to form a radical polymerizable layer in the hydrophilic layer. It is prepared by bonding a group and an unsaturated group on the substrate surface by a polymerization reaction. The hydrophilic layer has an extremely low thermal conductivity as compared with aluminum.

[Explanation of Hydrophilic Layer] As the hydrophilic polymer having a radical polymerizable group in the side chain to be contained in the hydrophilic layer of the lithographic printing plate precursor of the present invention, a vinyl group, an allyl group, (meth) acrylic It is a radical polymerizable group-containing hydrophilic polymer into which an ethylene addition polymerizable unsaturated group such as a group is introduced. These can be synthesized by the following method. (1) a method of copolymerizing a hydrophilic monomer and a monomer having an ethylene addition polymerizable unsaturated group, (2) a method of copolymerizing a hydrophilic monomer and a monomer having a double bond precursor, and then treating with a base or the like. Examples include a method of introducing a double bond, and (3) a reaction between a functional group of a hydrophilic polymer and a monomer having an ethylene addition-polymerizable unsaturated group. A particularly preferred method is a method of reacting a functional group of a hydrophilic polymer with a monomer having an ethylene-addition-polymerizable unsaturated group from a synthetic viewpoint.

The hydrophilic monomers used for synthesizing the hydrophilic polymer having a radical polymerizable group in the side chain include:
(Meth) acrylic acid or its alkali metal salt and amine salt, itaconic acid or its alkali metal salt and amine salt, 2-hydroxyethyl (meth) acrylate, (meth) acrylamide, N-monomethylol (meth) acrylamide, N- Dimethylol (meth) acrylamide, allylamine or its hydrohalide, 3-vinylpropionic acid or its alkali metal salt and amine salt, vinylsulfonic acid or its alkali metal salt and amine salt, 2-sulfoethyl (meth)
Carboxyl, sulfonic, phosphoric, and amino groups such as acrylate, polyoxyethylene glycol mono (meth) acrylate, 2-acrylamido-2-methylpropanesulfonic acid, and acid phosphooxypolyoxyethylene glycol mono (meth) acrylate Alternatively, a monomer having a hydrophilic group such as a salt thereof, a hydroxyl group, an amide group, and an ether group may be used.

The hydrophilic polymer includes a hydrophilic homo- or copolymer obtained by using at least one selected from the above hydrophilic monomers. Further, as an allyl group-containing monomer copolymerized with a hydrophilic monomer,
Allyl (meth) acrylate and 2-allyloxyethyl methacrylate are mentioned. Examples of the monomer having a double bond precursor include 2- (3-chloro-1-oxopropoxy) ethyl methacrylate. As a monomer having an addition-polymerizable unsaturated group used for introducing an unsaturated group by utilizing a reaction with a functional group such as a carboxyl group, an amino group or a salt thereof, a hydroxyl group and an epoxy group in a hydrophilic polymer. Examples include (meth) acrylic acid, glycidyl (meth) acrylate, allyl glycidyl ether, 2-isocyanatoethyl (meth) acrylate, and the like. The content of the hydrophilic polymer compound having a radical polymerizable group in the side chain to be contained in the hydrophilic layer is about 45 to 85% by weight, preferably 55 to 80% by weight, based on the total solid content of the hydrophilic layer. %. 45% by weight
Below, the hydrophilicity is insufficient and the performance as a non-image portion is reduced, and if it is 85% or more, the strength of the intermediate layer is insufficient and the printing durability is reduced, which is not suitable.

(Photopolymerization initiator) In the case where a radically polymerizable group of the hydrophilic polymer in the hydrophilic layer of the lithographic printing plate precursor according to the present invention and an unsaturated group on the substrate are polymerized by, for example, full-surface exposure to ultraviolet light. It is preferable that a photopolymerization initiator is contained in the component of the hydrophilic layer. At that time, as the photopolymerization initiator used, US Pat. No. 2,760,863,
No. 3,060,023, JP-A-62-212448
And the like. In the hydrophilic layer of the present invention, the content of the photopolymerization initiator is preferably 0.01 to 20% by weight based on the total solid content of the hydrophilic layer. If the amount is less than 0.01% by weight, the effect of the photopolymerization initiator cannot be exerted. If the amount is more than 20% by weight, the self-absorption of the actinic ray by the initiator makes it difficult for light to reach the inside and the desired printing durability is exhibited. Can not.

The thickness of the hydrophilic layer of the lithographic printing plate precursor according to the invention is preferably from 0.05 to 50 μm, more preferably from 0.1 to 10 μm. When the thickness is less than 0.05 μm, the hydrophilic heat insulating effect is not obtained. On the other hand, when the thickness is more than 50 μm, the film becomes brittle and the printing durability deteriorates.

[Description of Surface of Substrate Having Unsaturated Group] Next, the hydrophilic polymer compound chain having a radical polymerizable group in the side chain in the hydrophilic layer, which is a feature of the lithographic printing plate precursor of the present invention, is directly As a means for preparing a substrate surface chemically bonded to, for example, a liquid composition (sol liquid) containing a compound having an unsaturated group (a silane coupling agent) on an aluminum support is applied. After drying, a substrate having an unsaturated group retained on the surface of the support is produced. By using the substrate, the radical polymerizable group in the hydrophilic layer and the unsaturated group on the substrate surface can be chemically bonded by a photopolymerization reaction. The substrate surface of the lithographic printing plate precursor refers to a surface suitable for chemically bonding a hydrophilic polymer compound chain having a radical polymerizable group in a side chain to the surface, and exhibits this function. Any form is possible as far as possible.
It may be a layer separately provided on the support of the lithographic printing plate precursor according to the invention.

(Regarding the sol liquid) In general, a form in which an addition-reactive functional group is fixed to an inorganic polymer containing -Si-O-Si- bonds obtained by hydrolyzing and polycondensing a silane coupling agent. The sol-gel method (hereinafter, referred to as SG method) comprising the use of the organic-inorganic composite described above is preferably applied. The SG method is described in [Latest Technology of Organosilicon Polymers] (Chapter 6, Research Trends of Sol-Gel Method and Silicon Polymers, written by Yoshio Imai, CMC, 1996) and [Science of Sol-Gel Method] Husband, Agune Shofusha, 198
8) and the like, but the invention is not limited only to the above-mentioned documents and the like. The use of the SG method is preferable because the distribution of the addition-reactive functional groups bonded and immobilized on the substrate surface is hardly influenced by the distribution of chemical properties such as acid sites and base sites on the substrate surface.

The silane coupling agent used in the present invention includes a compound represented by the following general formula.

Ra (Rb) SiRc (Rd)

(At least two of Ra to Rd represent an alkoxy group or a -OCOR 'group having 10 or less carbon atoms, the other represents an addition-polymerizable reactive group, and R' represents an alkyl group.) Examples of the alkyl group represented by R ′ include a methyl group, an ethyl group, and a propyl group. Examples of the addition-polymerizable reactive group include an alkenyl group and an alkynyl group. Various linking groups may be bonded between the groups.
Examples of the alkenyl group include a vinyl group, a propenyl group, an allyl group, a butenyl group, and a dialkylmaleimide group.Examples of the alkynyl group include an acetylene group and an alkylacetylene group, but are not limited thereto. It is not something to be done. As silane coupling agents, [Silane Coupling Agents] (Edwin P. Plueddeman
n, Plemum Press, 1982).

Specifically, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetra (n-propoxy) silane, tetra (n-butoxy)
Examples include silane, tetrakis (2-ethylbutoxy) silane, tetrakis (2-ethylhexyloxy) silane, tetrakis (2-methoxyethoxy) silane, tetraphenoxysilane, tetraacetoxysilane, and the like, with tetraethoxysilane being particularly preferred. As the silane coupling agent having an addition-polymerizable ethylenic double bond reactive group, specifically,

[0026] _{CH 2 = CH-Si (OCOCH} 3) 3, CH 2 = CH-Si (OC 2 H 5) 3, CH 2 = CH-Si (OCH 3) 3, CH 2 = CHCH 2 -Si (OC _{2 H 5) 3, CH 2} = CHCH 2 NH (CH 2) 3 -Si (OCH 3) 3, CH 2 = CHCOO- (CH 2) 3 -Si (OCH 3) 3, CH 2 = CHCOO- (CH _{2) 3 -Si (OC 2 H} 5) 3, CH 2 = CHCOO- (CH 2) 4 -Si (OCH 3) 3, CH 2 = C (CH 3) COO- (CH 2) 3 -Si (OCH
_{3) 3, CH 2 = C} (CH 3) COO- (CH 2) 3 -Si (OC 2
_{H 5) 3, CH 2 =} C (CH 3) COO- (CH 2) 4 -Si (OCH
_{3) 3, CH 2 = C} (CH 3) COO- (CH 2) 5 -Si (OCH
_{3) 3, (CH 2 =} C (CH 3) COO- (CH 2) 3) 2 -Si
_{(OCH 3) 2, CH 2} = C (CH = CH 2) -Si (OCH 3) 3, CH 2 = CH-SO 2 NH- (CH 2) 3 -Si (OC
H ₃ ) ₃ , CH ₂ ＣＨCH-ph-O-Si (OCH ₃ ) ₃ (where ph represents a benzene ring)

CH ₂ ＣＨCH-ph-CONH- (CH ₂ ) ₃ —Si (O
_{CH 3) 3, CH 2 =} CH-ph-CH 2 NH- (CH 2) 3 -Si (O
_{CH 3) 3, CH 2 =} CH-ph-CH 2 NH-C 2 H 4 NH (CH 2) 3
-Si (OCH ₃ ) ₃ .HCl HC≡C-Si (OC ₂ H ₅ ) ₃ , CH ₃ C≡C-Si (OC ₂ H ₅ ) ₃ , DMI- (CH ₂ ) _m -CONH- (CH ₂ ) ₃ -Si (O
CH ₃ ) ₃ , (DMI: dimethylmaleimide group, m = 1 to 2
_{0) CH 2 = CHCH 2 O} -Si (OCH 3) 3, (CH 2 = CHCH 2 O) 4 Si, HO-CH 2 -C≡C-Si (OC 2 H 5) 3, CH 3 CH 2 CO —C≡C—Si (OC ₂ H ₅ ) ₃ , CH ₂ ＣＨCHS— (CH ₂ ) ₃ —Si (OCH ₃ ) ₃ , CH ₂ ＣＨCHCH ₂ O— (CH ₂ ) ₂ —SCH ₂ —Si ( O
_{CH 3) 3, CH 2 =} CHCH 2 S- (CH 2) 3 -S-Si (OC
_{H 3) 3, (CH 3} ) 3 CCO-C≡C-Si (OC 2 H 5) 3, (CH 2 = CH) 2 N- (CH 2) 2 -SCH 2 -Si (O
_{CH 3) 3, CH 3 COCH} = C (CH 3) -O-Si (OCH 3) 3

Examples include, but are not limited to: The silane coupling agent may be used by mixing several compounds in an arbitrary ratio. In addition, a known catalyst can be used to promote the reaction. The catalyst used is hydrochloric acid, sulfuric acid, nitric acid,
Mineral acids such as phosphoric acid, organic acids such as acetic acid, malic acid and oxalic acid, or bases such as ammonia, tetramethylammonium hydroxide, potassium hydroxide and sodium hydroxide can be used.

Next, the lithographic printing plate precursor according to the present invention is characterized in that the polymer having at least one group selected from the group consisting of a carboxylic acid group and a carboxylic acid group, on the hydrophilic layer, which causes decarboxylation by heat. The recording layer containing is described. The polymer having at least one group selected from the group consisting of a carboxylic acid group and a carboxylate group, which is contained in the recording layer of the lithographic printing plate precursor according to the invention is not particularly limited, but is represented by the following general formulas (1) and (1). It is preferably at least one selected from the group represented by 2). More preferably, the following general formula (2)
Is a polymer selected from the group consisting of carboxylate groups represented by The reason why the polymer selected from the group consisting of carboxylic acid groups is more preferable is that the developability is better.

[0030]

Embedded image

(Wherein X is selected from the group consisting of elements of Groups 4 to 6, oxides, sulfides, selenides and tellurides, P represents a polymer main chain, and -L- Represents a divalent linking group, R ¹ and R ² each represent a monovalent group which may be the same or different, M represents an alkali metal,
Represents any one selected from the group consisting of alkaline earth metals and onium. )

R¹, R^TwoAs monovalent non-gold containing hydrogen
Group is used, and a preferable example is a halogen atom.
(-F, -Br, -Cl, -I), a hydroxyl group,
Alkyl group, alkoxy group, aryloxy group, mercap
G, alkylthio, arylthio, alkyldithio
O group, aryldithio group, amino group, N-alkylamido
Group, N, N-diarylamino group, N-alkyl-N
-Arylamino group, acyloxy group, carbamoylo
Xy group, N-alkylcarbamoyloxy group, N-ali
Carbamoyloxy group, N, N-dialkylcarba
Moyloxy group, N, N-diarylcarbamoyloxy
S group, N-alkyl-N-arylcarbamoyloxy
Group, alkylsulfoxy group, arylsulfoxy group,
Silthio group, acylamino group, N-alkyl acylamido
Group, N-arylacylamino group, ureido group, N '
-Alkyl ureido group, N ', N'-dialkyl urea
Group, N'-arylureido group, N ', N'-diali
Ureido group, N'-alkyl-N'-aryluree
Id group, N-alkyl ureido group, N-aryl ureide
Group, N'-alkyl-N-alkylureido group, N '
-Alkyl-N-arylureido group, N ', N'-di
Alkyl-N-alkylureido group, N ', N'-dia
Alkyl-N-arylureido group, N'-aryl-N
-Alkyl ureido group, N'-aryl-N-aryl
Ureido group, N ', N'-diaryl-N-alkyl
RAID group, N ', N'-diaryl-N-aryluree
Id group, N'-alkyl-N'-aryl-N-alkyl
Luureido group, N'-alkyl-N'-aryl-N-
Arylureido group, alkoxycarbonylamino group,
Aryloxycarbonylamino group, N-alkyl-N-
Alkoxycarbonylamino group, N-alkyl-NA
Reyloxycarbonylamino group, N-aryl-NA
Lucoxycarbonylamino group, N-aryl-N-ali
-Carbonyloxyamino group, formyl group, acyl group,
Carboxyl group, alkoxycarbonyl group, aryloxy
Sicarbonyl group, carbamoyl group, N-alkylcarba
Moyl group, N, N-dialkylcarbamoyl group, N-A
Reel carbamoyl group, N, N-diarylcarbamoy
Group, N-alkyl-N-arylcarbamoyl group,
Rukylsulfinyl group, arylsulfinyl group,
Killsulfonyl group, arylsulfonyl group, sulfo group
(-SO_ThreeH) and its conjugated base group (hereinafter, sulfonato
Group), alkoxysulfonyl group, aryloxys
Ruphonyl group, sulfinamoyl group, N-alkyl sulf
Inamoyl group, N, N-dialkylsulfinamoyl
Group, N-arylsulfinamoyl group, N, N-diali
Sulfinamoyl group, N-alkyl-N-aryl
Sulfinamoyl group, sulfamoyl group, N-alkyl
Sulfamoyl group, N, N-dialkylsulfamoyl
Group, N-arylsulfamoyl group, N, N-diary
Rusulfamoyl group, N-alkyl-N-arylsul
Famoyl group, phosphono group (-PO_ThreeH_Two) And both
Role base group (hereinafter referred to as phosphonate group), dialkyl
A phosphono group (-PO_Three(alkyl) _Two), Diarylphosph
Ono group (-PO_Three(aryl)_Two), Alkyl aryl phospho
No group (-PO_Three(alkyl) (aryl)), monoalkylphospho
No group (-PO_ThreeH (alkyl)) and its conjugated base group (hereinafter, referred to as H (alkyl))
Alkylphosphonato group), monoarylphosphine
Ono group (-PO_ThreeH (aryl)) and its conjugate base group (hereinafter
Hereinafter referred to as an arylphosphonato group),
Group (-OPO_ThreeH_Two) And its conjugated base group (hereinafter referred to as phos
Phonatooxy group), dialkylphosphonooxy
Group (-OPO_Three(alkyl)_Two), Diarylphosphono
Xy group (-OPO_Three(aryl)_Two), Alkyl aryl phosph
Onoxy group (-OPO_Three(alkyl) (aryl)), monoalkyl
Ruphosphonooxy group (-OPO_ThreeH (alkyl)) and its
Conjugated base group (hereinafter referred to as alkylphosphonatooxy group)
), Monoarylphosphonooxy group (-OPO_ThreeH
(aryl)) and its conjugated base group (hereinafter, arylphospho)
Natoxy group), cyano group, nitro group, aryl
Group, alkenyl group and alkynyl group.

Specific examples of preferred alkyl groups include linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms which may have a substituent. Examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl,
Dodecyl group, tridecyl group, hexadecyl group, octadecyl group, eicosyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group,
Examples thereof include a 2-ethylhexyl group, a 2-methylhexyl group, a cyclohexyl group, a cyclopentyl group, and a 2-norbornyl group. Among these, straight-chain having 1 to 12 carbon atoms, branched having 3 to 12 carbon atoms,
Further, a cyclic alkyl group having 5 to 10 carbon atoms is more preferable.

Examples of the substituent of the substituted alkyl group
Is preferably a monovalent non-metallic atomic group other than hydrogen.
Examples include halogen atoms (-F, -Br, -Cl,
-I), hydroxyl group, alkoxy group, aryloxy
Group, mercapto group, alkylthio group, arylthio group,
Alkyldithio group, aryldithio group, amino group, N-
Alkylamino group, N, N-diarylamino group, N-
Alkyl-N-arylamino group, acyloxy group,
Rubamoyloxy group, N-alkylcarbamoyloxy
Group, N-arylcarbamoyloxy group, N, N-dia
Alkylcarbamoyloxy group, N, N-diarylcar
Bamoyloxy group, N-alkyl-N-arylcarba
Moyloxy group, alkyl sulfoxy group, aryl sulf
Oxy, acylthio, acylamino, N-alkyl
Luacylamino group, N-arylacylamino group, urea
Id group, N'-alkylureido group, N ', N'-dia
Alkyl ureido group, N'-aryl ureido group, N ',
N'-diarylureido group, N'-alkyl-N'-
Arylureido group, N-alkylureido group, NA
Reelureido group, N'-alkyl-N-alkyluree
An id group, an N'-alkyl-N-arylureido group,
An N ′, N′-dialkyl-N-alkylureido group,
An N ′, N′-dialkyl-N-arylureido group,
N'-aryl-N-alkylureido group, N'-ali
-N-arylureido group, N ', N'-diary
Ru-N-alkylureido group, N ', N'-diaryl
-N-arylureido group, N'-alkyl-N'-a
Reel-N-alkylureido group, N'-alkyl-
N'-aryl-N-arylureido group, alkoxy
Carbonylamino group, aryloxycarbonylamino
Group, N-alkyl-N-alkoxycarbonylamino
Group, N-alkyl-N-aryloxycarbonylamino
Group, N-aryl-N-alkoxycarbonylamino
Group, N-aryl-N-aryloxycarbonylamino
Group, formyl group, acyl group, carboxyl group, alkoxy
Cicarbonyl group, aryloxycarbonyl group, carbamo
Yl group, N-alkylcarbamoyl group, N, N-dial
A kill carbamoyl group, an N-aryl carbamoyl group,
N, N-diarylcarbamoyl group, N-alkyl-N
-An arylcarbamoyl group, an alkylsulfinyl group,
Arylsulfinyl group, alkylsulfonyl group, ant
Sulfonyl group, sulfo group (—SO_ThreeH) and both
Role base group (hereinafter referred to as sulfonato group), alkoxys
Ruphonyl group, aryloxysulfonyl group, sulfinamo
Yl group, N-alkylsulfinamoyl group, N, N-di
Alkylsulfinamoyl group, N-arylsulfina
Moyl group, N, N-diarylsulfinamoyl group, N
-Alkyl-N-arylsulfinamoyl group, sulf
Amoyl group, N-alkylsulfamoyl group, N, N-
Dialkylsulfamoyl group, N-arylsulfamo
Yl group, N, N-diarylsulfamoyl group, N-A
Alkyl-N-arylsulfamoyl group, phosphono group
(-PO_ThreeH_Two) And its conjugated base group (hereinafter referred to as phosphona
A dialkylphosphono group (—PO_Three(alky
l)_Two), A diarylphosphono group (—PO_Three(aryl)_Two),
Alkylarylphosphono group (-PO_Three(alkyl) (ary
l)), monoalkylphosphono group (-PO_ThreeH (alkyl))
And its conjugated base group (hereinafter referred to as alkylphosphonate group)
), Monoarylphosphono group (-PO_ThreeH (ary
l)) and its conjugated base group (hereinafter, arylphosphonate)
Group), a phosphonooxy group (-OPO_ThreeH_Two)as well as
Its conjugated base group (hereinafter referred to as phosphonatoxy group)
), A dialkylphosphonooxy group (-OPO_Three(alky
l)_Two), Diarylphosphonooxy group (—OPO_Three(ary
l) _Two), An alkylarylphosphonooxy group (—OP
O_Three(alkyl) (aryl)), monoalkylphosphonooxy group
(-OPO_ThreeH (alkyl)) and its conjugate base group (hereinafter a
Alkylphosphonatooxy group)
Sulfonooxy group (-OPO_ThreeH (aryl)) and its conjugate
A base group (hereinafter referred to as an arylphosphonatooxy group)
), Cyano group, nitro group, aryl group, alkenyl
And alkynyl groups.

In these substituents, specific examples of the alkyl group include the aforementioned alkyl groups, and specific examples of the aryl group include phenyl, biphenyl, naphthyl, tolyl, xylyl, and mesityl groups. , Cumenyl, chlorophenyl, bromophenyl, chloromethylphenyl, hydroxyphenyl, methoxyphenyl, ethoxyphenyl, phenoxyphenyl, acetoxyphenyl, benzoyloxyphenyl, methylthiophenyl, phenylthiophenyl A methylaminophenyl group, a dimethylaminophenyl group, an acetylaminophenyl group, a carboxyphenyl group, a methoxycarbonylphenyl group, an ethoxyphenylcarbonyl group,
Examples thereof include a phenoxycarbonylphenyl group, an N-phenylcarbamoylphenyl group, a phenyl group, a cyanophenyl group, a sulfophenyl group, a sulfonatophenyl group, a phosphonophenyl group, and a phosphonatophenyl group. Examples of the alkenyl group include a vinyl group, 1
-Propenyl group, 1-butenyl group, cinnamyl group, 2-
Examples thereof include a chloro-1-ethenyl group, and examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 1-butynyl group, and a trimethylsilylethynyl group.
Examples of G ¹ in the acyl group (G ¹ CO—) include hydrogen and the above-described alkyl and aryl groups. Of these substituents, still more preferred are a halogen atom (-F, -Br, -Cl, -I), an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an N-alkylamino group, an N, N- Dialkylamino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl Group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group,
N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonato group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N-alkyl-N
An arylsulfamoyl group, a phosphono group, a phosphonate group, a dialkylphosphono group, a diarylphosphono group, a monoalkylphosphono group, an alkylphosphonato group, a monoarylphosphono group, an arylphosphonato group, a phosphonooxy group, Examples include a phosphonatoxy group, an aryl group, and an alkenyl group.

On the other hand, the alkylene group in the substituted alkyl group may be a divalent organic residue obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. And preferably a linear alkylene group having 1 to 12 carbon atoms, a branched alkylene group having 3 to 12 carbon atoms and a cyclic alkylene group having 5 to 10 carbon atoms. Preferred specific examples of the substituted alkyl group obtained by combining the substituent with an alkylene group include chloromethyl group, bromomethyl group, 2-chloroethyl group, trifluoromethyl group, methoxymethyl group, methoxyethoxyethyl group, and allyl. Oxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl group, N- Phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxycarbonylethyl group, allyloxy Rubonirubuchiru group, chlorophenoxy carbonyl methyl group, a carbamoylmethyl group, N- methylcarbamoyl ethyl, N, N- dipropylcarbamoylmethyl group, N
-(Methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) carbamoylmethyl group,
Sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N
-Dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N-methyl-N- (phosphonophenyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, Diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group, tolylphosphonohexyl group, tolylphosphonatohexyl group, phosphonooxypropyl group, phosphonatoxybutyl group, benzyl group, phenethyl group, α- Methylbenzyl group, 1-methyl-1-phenylethyl group, p-methylbenzyl group, cinnamyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2
-Methylpropenylmethyl group, 2-propynyl group, 2-
Butynyl group, 3-butynyl group and the like.

Examples of the aryl group include a group in which one to three benzene rings form a condensed ring, and a group in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. Phenyl group, naphthyl group, anthryl group,
Phenanthryl group, indenyl group, acenaphthenyl group,
Examples thereof include a fluorenyl group and the like, and among these, a phenyl group and a naphthyl group are more preferable. The aryl group includes a heterocyclic (hetero) aryl group in addition to the carbocyclic aryl group. Examples of the heterocyclic aryl group include a pyridyl group, a furyl group, and other quinolyl, benzofuryl, thioxanthone, and carbazole groups each having 3 to 20 carbon atoms and 1 to 5 heteroatoms such as a benzene ring condensed. Used.

As the substituted aryl group, those having a monovalent nonmetallic atomic group other than hydrogen as a substituent on the ring-forming carbon atom of the aforementioned aryl group are used. Examples of preferred substituents include the aforementioned alkyl groups, substituted alkyl groups,
In addition, there can be mentioned those described above as the substituent in the substituted alkyl group. Preferred specific examples of such substituted aryl groups include biphenyl, tolyl, xylyl, mesityl, cumenyl, chlorophenyl, bromophenyl, fluorophenyl, chloromethylphenyl, and trifluoromethylphenyl. ,
Hydroxyphenyl, methoxyphenyl, methoxyethoxyphenyl, allyloxyphenyl, phenoxyphenyl, methylthiophenyl, tolylthiophenyl, ethylaminophenyl, diethylaminophenyl, morpholinophenyl, acetyloxyphenyl, benzoyl Oxyphenyl group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxy Carbonylphenyl group, carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N (Methoxyphenyl) carbamoylphenyl group, N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N- Dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenyl Phosphonophenyl group, methylphosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonatophenyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallylphenyl group, 2-methylpro Nirufeniru group, 2-propynyl phenyl group, 2-butynyl phenyl group, and a 3-butynylphenyl group.

Preferred examples of -X- are -O-, -S
-, - Se -, - NR 3 -, - CO -, - SO -, - S
O ₂ — and —PO— are represented. Among them, -CO from the viewpoint of heat reactive -, - SO -, - SO 2 - is particularly preferred.
Specific examples of preferred R ³ may be different be the same as R ¹ and R ^2, it can be selected from R ¹ and R ² embodiments.

The divalent linking group represented by L includes 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 100 Up to hydrogen atoms and 0 to 20 sulfur atoms. More specific examples of the linking group include those constituted by combining the following structural units.

[0041]

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M is not particularly limited as long as it is a cation, but is preferably a monovalent to tetravalent metal cation or an ammonium salt represented by the following general formula (3).

[0043]

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(R ⁴ , R ⁵ , R ⁶ and R ⁷ each represent a monovalent group which may be the same or different.)

The metal cations of 1-4 represented by M include Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , Cs ⁺ , Fr ⁺ , B
e ²⁺ , Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Ra ²⁺ , Cu
^{+, Cu 2 +, Ag +} , Zn 2+, Al 3+, Fe 2+, Fe 3+,
Co ²⁺ , Ni ²⁺ , Ti ⁴⁺ and Zr ⁴⁺ can be mentioned. More preferably, Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , C
Examples include s ⁺ , Fr ⁺ , Cu ⁺ , and Ag ⁺ .

In the ammonium ion represented by the general formula (3), specific examples of the groups represented by R ^{4 to} R ⁷ include the same groups as those represented by R ^{1 to} R ^3. Can be Specific examples of the ammonium ion represented by the general formula (3) include the following.

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The polymer main chain represented by P is selected from at least one of partial structural groups represented by the following general formula.

[0049]

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In the present invention, the polymer having at least one group selected from the group consisting of a carboxylic acid group and a carboxylic acid group may be a homopolymer of only one monomer, or a copolymer of two or more monomers. May be.
As the monomer used in the synthesis of the polymer having at least one group selected from the group consisting of a carboxylic acid group and a carboxylic acid group in the present invention, those exemplified in the following specific examples are preferable.

[0051]

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[0052]

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[0053]

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The polymer having at least one group selected from the group consisting of a carboxylic acid group and a carboxylic acid group in the present invention may be a copolymer of the above-mentioned monomer and another monomer. As other monomers used, for example, acrylates, methacrylic esters, acrylamides, methacrylamides, vinyl esters, styrenes, acrylic acid, methacrylic acid, acrylonitrile, maleic anhydride, maleic imide and the like Known monomers are also included. By copolymerizing such monomers, various physical properties such as film forming property, film strength, hydrophilicity, hydrophobicity, solubility, reactivity, and stability can be improved.

Specific examples of the acrylates include:
Methyl acrylate, ethyl acrylate, (n- or i-) propyl acrylate, (n-, i-, sec-
Or t-) butyl acrylate, amyl acrylate,
2-ethylhexyl acrylate, dodecyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate,
2-hydroxypentyl acrylate, cyclohexyl acrylate, allyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, benzyl acrylate, methoxybenzyl acrylate, chlorobenzyl acrylate, hydroxybenzyl acrylate, hydroxyphenethyl acrylate, dihydroxyphenethyl acrylate, furfuryl acrylate, Examples thereof include tetrahydrofurfuryl acrylate, phenyl acrylate, hydroxyphenyl acrylate, chlorophenyl acrylate, sulfamoylphenyl acrylate, and 2- (hydroxyphenylcarbonyloxy) ethyl acrylate.

Specific examples of the methacrylates include methyl methacrylate, ethyl methacrylate,
(N- or i-) propyl methacrylate, (n-, i
-, Sec- or t-) butyl methacrylate, amyl methacrylate, 2-ethylhexyl methacrylate,
Dodecyl methacrylate, chloroethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxypentyl methacrylate, cyclohexyl methacrylate, allyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate,
Benzyl methacrylate, methoxybenzyl methacrylate, chlorobenzyl methacrylate, hydroxybenzyl methacrylate, hydroxyphenethyl methacrylate, dihydroxyphenethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, hydroxyphenyl methacrylate, chlorophenyl methacrylate, sulfamoylphenyl methacrylate, 2- (Hydroxyphenylcarbonyloxy) ethyl methacrylate and the like.

Specific examples of acrylamides include acrylamide, N-methylacrylamide, N-ethylacrylamide, N-propylacrylamide, N-butylacrylamide, N-benzylacrylamide, and N-benzylacrylamide.
Hydroxyethylacrylamide, N-phenylacrylamide, N-tolylacrylamide, N- (hydroxyphenyl) acrylamide, N- (sulfamoylphenyl) acrylamide, N- (phenylsulfonyl)
Acrylamide, N- (tolylsulfonyl) acrylamide, N, N-dimethylacrylamide, N-methyl-
N-phenylacrylamide, N-hydroxyethyl-
N-methylacrylamide and the like can be mentioned.

Specific examples of methacrylamides include methacrylamide, N-methyl methacrylamide, N-ethyl methacrylamide, N-propyl methacrylamide, N-butyl methacrylamide, N-benzyl methacrylamide, N-hydroxyethyl methacryl Amide,
N-phenylmethacrylamide, N-tolylmethacrylamide, N- (hydroxyphenyl) methacrylamide, N- (sulfamoylphenyl) methacrylamide, N- (phenylsulfonyl) methacrylamide, N
-(Tolylsulfonyl) methacrylamide, N, N-dimethylmethacrylamide, N-methyl-N-phenylmethacrylamide, N-hydroxyethyl-N-methylmethacrylamide and the like.

Specific examples of vinyl esters include vinyl acetate, vinyl butyrate, vinyl benzoate and the like. Specific examples of styrenes include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, propylstyrene, cyclohexylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, methoxystyrene, dimethoxystyrene , Chlorostyrene, dichlorostyrene, bromostyrene, iodostyrene, fluorostyrene, carboxystyrene and the like.

The proportion of these other monomers used in the synthesis of the copolymer must be sufficient to improve various physical properties, but if the proportion is too large, the carboxylic acid or carboxylate may be used. The function of the monomer containing is insufficient. Therefore, the preferable total ratio of the other monomers is preferably 80% by weight or less, more preferably 50% by weight or less.

Hereinafter, specific examples of the polymer having at least any one group selected from the group consisting of a carboxylic acid group and a carboxylate group which cause decarboxylation by heat in the present invention are shown below.

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[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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The recording layer of the lithographic printing plate precursor according to the present invention is described in JP-A-62-251740 and JP-A-3-208514 in order to expand stability under printing conditions. Such nonionic surfactants and amphoteric surfactants described in JP-A-59-121044 and JP-A-4-13149 can be added. Specific examples of nonionic surfactants include
Sorbitan tristearate, sorbitan monopalmitate, sorbitan triolate, monoglyceride stearate, polyoxyethylene nonyl phenyl ether and the like can be mentioned. Specific examples of the amphoteric surfactant include alkyldi (aminoethyl) glycine, alkylpolyaminoethylglycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine and N-tetradecyl-N, N- Betaine type (for example,
(Trade name: Amogen K, manufactured by Dai-ichi Kogyo Co., Ltd.). The proportion of the nonionic surfactant and amphoteric surfactant in the total solids in the recording layer is 0.05 to 15% by weight.
And more preferably 0.1 to 5% by weight.

Further, a plasticizer may be added to the recording layer of the lithographic printing plate precursor according to the invention, if necessary, in order to impart flexibility to the coating film. For example, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, oligomers of acrylic acid or methacrylic acid And a polymer.

The recording layer of the lithographic printing plate precursor according to the present invention can be usually produced by dissolving each of the above-mentioned components in a solvent and applying the resultant solution on the hydrophilic layer. As the solvent used here, ethylene dichloride, cyclohexanone, methyl ethyl ketone, methanol, ethanol, propanol, ethylene glycol monomethyl ether,
1-methoxy-2-propanol, 2-methoxyethyl acetate, 1-methoxy-2-propyl acetate,
Dimethoxyethane, methyl lactate, ethyl lactate, N, N-
Dimethylacetamide, N, N-dimethylformamide, tetramethylurea, N-methylpyrrolidone, dimethylsulfoxide, sulfolane, γ-butyrolactone,
Examples include toluene and water, but are not limited thereto. These solvents are used alone or as a mixture. The concentration of the above components (total solids including additives) in the solvent is preferably 1 to 50% by weight. The coating amount (solid content) of the recording layer on the hydrophilic layer obtained after coating and drying is generally preferably from 0.5 to 5.0 g / m ² . Various methods can be used as the method of coating, and examples thereof include bar coater coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating, and roll coating.

In the recording layer of the lithographic printing plate precursor according to the present invention, a surfactant for improving coating properties, such as a fluorine-based surfactant described in JP-A-62-170950, is used. Agents can be added. The preferred amount is 0.01 to 1% by weight, more preferably 0.05 to 0.5% by weight, based on the total solid content of the recording layer.

[Support] The support used in the lithographic printing plate precursor according to the invention is not limited as long as it has an unsaturated group on its surface or can introduce an unsaturated group as described above. Although not particularly limited, it is a dimensionally stable plate-like material such as paper, paper laminated with plastic (eg, polyethylene terephthalate, polyethylene, polypropylene, polystyrene, etc.), and metal plate (eg, aluminum, zinc) , Copper, etc.), plastic films (eg, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.) Like metal is lamine Is collected by or deposited, paper or plastic films.

The preferred aluminum plate used in the present invention is a pure aluminum plate and aluminum as a main component,
It may be an alloy plate containing a trace amount of a different element, or a plastic film on which aluminum is laminated or vapor-deposited. The foreign elements contained in aluminum alloys include silicon, iron, manganese, copper, magnesium, chromium, zinc,
Examples include bismuth, nickel, and titanium. The content of the foreign element in the alloy is at most 10% by weight or less. Aluminum which is particularly preferred in the present invention is pure aluminum. However, completely pure aluminum is difficult to produce due to refining technology, and therefore may contain a slightly different element. As described above, the composition of the aluminum plate applied to the present invention is not specified, and an aluminum plate of a conventionally known and used material can be appropriately used. The thickness of the aluminum plate used in the present invention is about 0.1 m
m to about 0.6 mm, preferably 0.15 mm to 0.4
mm, particularly preferably 0.2 mm to 0.3 mm.

(Photothermal Conversion Agent) When an image is formed on the lithographic printing plate precursor according to the present invention by scanning exposure with a laser beam or the like, light energy is applied to at least one of the hydrophilic layer and the recording layer. It is preferable to include a light-to-heat conversion agent for converting into heat energy. As the photothermal conversion agent that may be contained in the hydrophilic layer or the recording layer of the lithographic printing plate precursor according to the invention, a substance capable of absorbing light such as ultraviolet light, visible light, infrared light, and white light and converting it into heat can be used. All can be used, and examples thereof include carbon black, carbon graphite, pigments, phthalocyanine pigments, metal powders, metal compound powders, and the like. Particularly preferred is a wavelength 76
Dyes, pigments, metal powders, and metal compound powders that effectively absorb infrared rays from 0 nm to 1200 nm.

Examples of preferred infrared absorbing agents will be described below. [Infrared absorber] The infrared absorber preferably used in the present invention is a dye or pigment that effectively absorbs infrared rays having a wavelength of 760 nm to 1200 nm. More preferably, it is a dye or a pigment having an absorption maximum at a wavelength of 760 nm to 1200 nm. As the dye, commercially available dyes and known dyes described in literatures (for example, "Dye Handbook" edited by The Society of Synthetic Organic Chemistry, published in 1970) can be used.
Specifically, azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, anthraquinone dyes, phthalocyanine dyes,
Dyes such as a carbonium dye, a quinone imine dye, a methine dye, a cyanine dye, and a metal thiolate complex are exemplified.

Preferred dyes include, for example, those described in
125246, JP-A-59-84356, JP-A-5-84356
Cyanine dyes described in JP-A-9-202829 and JP-A-60-78787;
JP-A-58-181690, JP-A-58-194
No. 595, etc .;
Naphthoquinone dyes described in JP-A-112793, JP-A-58-224793, JP-A-59-48187, JP-A-59-73996, JP-A-60-52940, JP-A-60-63744, etc. JP-A-58-112
792 and the cyanine dyes described in British Patent No. 434,875.

Further, a near infrared absorption sensitizer described in US Pat. No. 5,156,938 is preferably used, and a substituted arylbenzo (thio) described in US Pat. No. 3,881,924 is also preferable. Pyrylium salt, JP-A-57-142645
No. (U.S. Pat. No. 4,327,169), trimethinethiapyrylium salts described in JP-A-58-181051, 58-220143, 59-41363, and 59.
Nos. -84248, 59-84249, 59-14
Nos. 6063 and 59-146061, pyranyl compounds, cyanine dyes described in JP-A-59-216146, pentamethine thiopyrylium salts described in U.S. Pat. No. 4,283,475, and the like. Fairness 5-13
Pyrylium compounds disclosed in JP-A-514 and JP-A-5-19702 are also preferably used. Another preferred example of the dye is U.S. Pat. No. 4,756,993.
Near-infrared absorbing dyes described in the specification as formulas (I) and (II) can be mentioned. Among these dyes, particularly preferred are cyanine dyes, squarylium dyes, pyrylium salts, and nickel thiolate complexes.

The pigment used in the present invention includes:
Commercial Pigment and Color Index (CI) Handbook, “Latest Pigment Handbook” (edited by Japan Pigment Technical Association, 1977)
Annual Publication), “Latest Pigment Application Technology” (CMC Publishing, 1986)
Pigments described in "Printing Ink Technology", CMC Publishing, 1984). Examples of the type of the pigment include a black pigment, a yellow pigment, an orange pigment, a brown pigment, a red pigment, a violet pigment, a blue pigment, a green pigment, a fluorescent pigment, a metal powder pigment, and a polymer-bound pigment. Specifically, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelated azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments And quinophthalone pigments, dyed lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, carbon black, and the like. Preferred among these pigments is carbon black.

These pigments may be used without surface treatment, or may be used after surface treatment. Examples of the surface treatment include a method of surface coating a resin or wax, a method of attaching a surfactant, and a method of condensing a reactive substance (for example, a silane coupling agent, an epoxy compound, or a polyisocyanate) on the pigment surface. Conceivable. The above surface treatment methods are described in “Properties and Applications of Metallic Soap” (Koshobo), “Printing Ink Technology” (CMC Publishing, 1984) and “Latest Pigment Application Technology” (CMC Publishing, 198).
6th edition).

The particle size of the pigment is preferably in the range of 0.01 μm to 10 μm, more preferably in the range of 0.05 μm to 1 μm, and particularly preferably in the range of 0.1 μm to 1 μm.
Is preferably within the range. Pigment particle size 0.01μ
If it is less than m, it is not preferable in terms of stability of the dispersion in a coating solution of the photosensitive composition, and if it exceeds 10 μm, it is not preferable in terms of uniformity of an image recording layer after coating. As a method for dispersing the pigment, a known dispersion technique used in the production of ink or toner can be used. Examples of the disperser include an ultrasonic disperser, a sand mill, an attritor, a pearl mill, a super mill, a ball mill, an impeller, a disperser, a KD mill, a colloid mill, a dynatron, a three-roll mill, and a pressure kneader. Details are described in "Latest Pigment Application Technology" (CMC Publishing, 1986).

When these dyes or pigments are contained in the recording layer of the lithographic printing plate precursor, 0.01 to 50% by weight, preferably 0.1 to 10% by weight, based on the total solid content of the recording layer, Is particularly preferably 0.5 to 10% by weight, and in the case of a pigment, 1.0 to 10% by weight can be particularly preferably added. When the amount of the pigment or dye added is 0.
When the amount is less than 01% by weight, the sensitivity is lowered, and when the amount exceeds 50% by weight, stains are apt to occur in the non-image area during printing.

[0083]

EXAMPLES The present invention will be described below in detail with reference to examples, but the scope of the present invention is not limited by these examples. [Production Example 1 of Hydrophilic Polymer] 18 g of polyacrylic acid (average molecular weight: 25,000) was dissolved in 300 g of DMAc, and 0.41 g of hydroquinone, 19.4 g of 2-methacryloyloxyethyl isocyanate and 0.25 g of dibutyltin dilaurate were added. At 65 ° C. for 4 hours. The acid value of the obtained polymer was 7.02 meq / g. The carboxyl group was neutralized with a 1N aqueous solution of sodium hydroxide, added to ethyl acetate to precipitate the polymer, and washed well to obtain a hydrophilic polymer.

Examples 1 to 6 (Method of Manufacturing Substrate Having Sol-Gel Layer) Thickness 0.30
The surface of an aluminum plate having a thickness of 0.5 mm was grained with a nylon brush and a 400 mesh aqueous suspension of pamistone, and then thoroughly washed with water. After etching by immersing in a 10% by weight aqueous solution of sodium hydroxide at 70 ° C. for 60 seconds, washing with running water, neutralizing and washing with 20% by weight nitric acid, and then washing with water. This was converted to 160% in a 1% by weight aqueous nitric acid solution using a sinusoidal alternating current under the condition of _VA = 12.7V.
The electrolytic surface-roughening treatment was performed with an amount of electricity at the anode of Coulomb / dm ² . The surface roughness was measured to be 0.6 μm (R
a). Subsequently, after immersing in a 30% by weight aqueous sulfuric acid solution and desmutting at 55 ° C. for 2 minutes, the thickness of the anodic oxide film was increased to 2.7 g / m ² at a current density of 2 A / dm ² in a 20% by weight aqueous sulfuric acid solution. Anodizing treatment was performed for 2 minutes.

Next, a liquid composition (sol liquid) of the sol-gel method was prepared according to the following procedure.

(Sol Solution) Methanol 130 g Water 20 g 85 wt% phosphoric acid 16 g Tetraethoxysilane 50 g 3-methacryloxypropyltrimethoxysilane 60 g

The sol liquid having the above composition was mixed and stirred. About 5
A fever was noted in minutes. After reacting for 60 minutes, the content was transferred to another container, and 3000 g of methanol was added to obtain a sol solution. This sol solution was diluted with methanol / ethylene glycol = 9/1 (weight ratio) and applied so that the amount of Si on the substrate was 3 mg / m ² ,
It dried at 1 degreeC for 1 minute, and produced the aluminum substrate.

(Formation of Hydrophilic Layer) A hydrophilic layer coating solution of the composition shown below was coated on the aluminum substrate thus treated, dried at 100 ° C. for 2 minutes, and exposed to UV to form a film having a thickness of 1.5.
A 5 μm hydrophilic layer was formed.

(Hydrophilic Layer Coating Solution) Hydrophilic polymer 1 (the above-mentioned substance) 1.0 g Photopolymerization initiator A (the following structure) 0.1 g Distilled water 12.7 g Acetonitrile 6.4 g

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(Formation of Recording Layer) Six kinds of the following recording layer coating liquids (A-1) to (C-1) were prepared by changing the type of the carboxylic acid (salt) group-containing polymer in the present invention as shown in Table 1 below.
(A-3) and (B-1) to (B-3) were prepared. Each of these recording layer coating solutions is applied on the hydrophilic layer, and
Dried at 00 ° C for 2 minutes, lithographic printing plate precursor (A-1)-
(A-3) and (B-1) to (B-3) were obtained. The weight after drying was 1.1 g / m ² .

[0092]

[Table 1]

(Recording Layer Coating Solutions A1 to 3) Carboxylic acid group-containing polymer (see Table 1) 1.0 g Infrared absorber NK-3508 (manufactured by Japan Photographic Dye Laboratories Co., Ltd.) 0.15 g fluorine-based Surfactant (F-177, manufactured by Dainippon Ink and Chemicals, Inc.) 0.06 g Methyl ethyl ketone 20 g Methanol 7 g

(Recording Layer Coating Solutions B1 to 3) Carboxylic acid group-containing polymer (see Table 1) 1.0 g High micron K black (manufactured by Sangoku Dye Co., Ltd.) 0.30 g water 18 g acetonitrile 9 g

(Printing Evaluation) The lithographic printing plate precursors obtained in Examples 1 to 6 were exposed to a semiconductor laser emitting infrared light having a wavelength of 830 nm. The exposed plate was printed on a Heidel KOR-D printing machine without development. The dampening solution is I
F201 (2.5%) and IF202 (0.75%) [manufactured by Fuji Photo Film Co., Ltd.] were used. The ink inking property of the image area was evaluated at the time of printing of 1,000 sheets and at the time of printing of 20,000 sheets. Further, the stainability of the non-image area was also evaluated. In each case, a good printed matter having no stain on the non-image area was obtained even after printing 20,000 sheets.

[Comparative Examples 1-2] A lithographic printing plate precursor was prepared in the same manner as in Examples 1-3 except that polyacrylic acid was used in place of the polymer having a carboxylic acid group used in Examples 1-3. (C-1) was obtained, and plate making and printing were performed. Further, a lithographic printing plate precursor (C-2) was obtained in the same manner as in Examples 4 to 6, except that sodium polyacrylate was used in place of the polymer having a carboxylate group used in Examples 4 to 6. Plate making and printing. In both (C-1) and (C-2), the ink adhesion of the rear part of the image was poor, and no printed matter was obtained.

[0097]

As described above, the lithographic printing plate precursor according to the present invention forms a surface containing a compound having an unsaturated group on a substrate, and radically polymerizes the unsaturated group of the substrate and the hydrophilic layer in the hydrophilic layer. A hydrophilic layer made of a material having a lower thermal conductivity than aluminum chemically bonded to the surface of the machine number, and decarboxylation by heat on the hydrophilic layer. Preparation of a lithographic printing plate precursor having a recording layer containing a polymer having at least any group selected from the group consisting of carboxylic acid groups and carboxylic acid groups, preferably a polymer selected from the group consisting of carboxylic acid groups By doing so, it is possible to suppress the diffusion of heat due to infrared laser exposure and the like in the recording layer, and to completely convert the solubility of the polymer compound in the recording layer in water, thereby reducing the energy Sufficient image formation is carried out in over the amount of IR laser irradiation, i.e. the effect of high sensitivity is obtained. In addition, since the hydrophilic layer is chemically bonded to the surface of the machine, even if it swells, the adhesion to the substrate does not deteriorate,
Even under severe printing conditions for a large number of sheets, a printed matter having good printing durability and no stain is obtained. Further, the lithographic printing plate precursor according to the present invention can be plate-formed and printed by a simple water-development operation after image recording, or directly mounted on a printing machine which does not require a development process.

 ──────────────────────────────────────────────────続 き Continued on front page F term (reference) 2H025 AA00 AA01 AA12 AA14 AB03 AC08 AD03 BF01 CC20 DA36 FA10 2H096 AA00 AA07 AA08 BA11 BA16 EA04 GA45 2H114 AA04 AA22 AA24 BA01 DA04 DA13 DA25 DA26 DA27 DA38 DA03 EA52 DA73 FA16 GA03 GA05 GA06 GA08 GA09 GA34 GA38

Claims (2)

[Claims] 1. A hydrophilic layer which contains a polymer compound having a hydrophilic group which is bonded to a substrate via a covalent bond and a carboxylic acid group which causes decarboxylation by heat on the hydrophilic layer. And a recording layer containing a polymer compound having at least any one group selected from the group consisting of carboxylate groups. 2. The lithographic printing method according to claim 1, wherein the polymer that causes decarboxylation by heat is at least one selected from the group represented by the following general formulas (1) and (2). The original for the edition. Embedded image (Wherein, X is selected from the group consisting of elements of Groups 4 to 6, oxides, sulfides, selenides and tellurides, P represents a polymer main chain, and -L- is divalent. Wherein R ¹ and R ² each represent a monovalent group which may be the same or different, and M represents any one selected from the group consisting of alkali metals, alkaline earth metals and onium. )