JP2005300817A - Polymerizable composition and lithographic printing master plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymerizable composition excellent in film strength and exhibiting high sensitivity, and a lithographic printing master plate excellent in printing durability and sensitivity and suitable for drawing by laser light. <P>SOLUTION: The polymerizable composition contains a polymerizable compound, a binder polymer, a polymerization initiator and a sensitizing dye, wherein at least one of components constituting the composition is a compound having an unshared electron pair and a hydrogen atom capable of hydrogen bonding and having a substituent capable of forming two or more hydrogen bonds. The lithographic printing master plate has on a support a photosensitive layer comprising the polymerizable composition. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a negative polymerizable composition and a lithographic printing plate precursor, and more particularly to a negative polymerizable composition and a lithographic printing plate precursor that can be written with high sensitivity by an infrared laser.

  Conventionally, as a method of forming an image by exposure of a photopolymerizable composition, a layer of a photopolymerizable composition comprising a polymer binder, an ethylenically unsaturated compound, a photopolymerization initiator, or further a sensitizing dye is supported. A method of forming a cured relief image by forming an image on the body surface, polymerizing and curing the ethylenically unsaturated compound in the exposed portion by exposing to light, and dissolving and removing the non-exposed portion is widely used. Many proposals have been made on various ethylenically unsaturated compounds, photopolymerization initiators, sensitizing dyes, and the like for the purpose of improving the sensitivity of the photopolymerizable composition. It was not satisfactory in terms of

Moreover, it is known that the curing efficiency is increased by using a copolymer of allyl (meth) acrylate as a binder polymer of the polymerizable composition (for example, see Patent Document 1). Polymerization using a polymer obtained by reacting a part of the carboxyl group of a carboxyl group-containing polymer with an epoxy group-containing ethylenically unsaturated compound and introducing an ethylenically unsaturated bond in the side chain as a binder polymer Compositions are also known (see, for example, Patent Document 2). However, the performance of these compositions is not sufficient, and further improvements have been desired in terms of printing durability and sensitivity.
Japanese Examined Patent Publication No. 3-63740 Japanese Patent Laid-Open No. 10-10719

  Accordingly, an object of the present invention is to provide a polymerizable composition exhibiting excellent film strength and high sensitivity, and a lithographic printing plate precursor excellent in printing durability and sensitivity and suitable for drawing with laser light. .

  As a result of intensive studies to achieve the above object, the present inventors have confirmed that the above object can be achieved by including a component having a specific hydrogen bonding functional group in the polymerizable composition. The headline and the present invention were made.

That is, the polymerizable composition of the present invention is a polymerizable composition containing a binder polymer, a polymerizable compound, a polymerization initiator, and a sensitizing dye,
At least one of the components constituting this includes a compound having a substituent that can form two or more hydrogen bonds, having a lone pair and a hydrogen atom capable of hydrogen bonding.
That is, the polymerizable composition of the present invention is composed of four essential components and an optional component, and at least one of these components has a lone pair and a hydrogen atom capable of hydrogen bonding. It is necessary to be a compound having a substituent capable of forming the above hydrogen bond.

  The lithographic printing plate precursor according to the invention is characterized in that a photosensitive layer containing the polymerizable composition according to the invention is provided on a support.

Although the operation of the present invention is not clear, it is presumed as follows.
In the present invention, the compound having a lone pair and a hydrogen atom capable of hydrogen bonding and having a substituent capable of forming two or more hydrogen bonds is capable of hydrogen bonding with the lone pair in the molecule. Since it has a hydrogen atom and a substituent that can form two or more hydrogen bonds (hereinafter, referred to as “multi-point hydrogen bonding group” as appropriate), these multi-point hydrogen bonding properties are included in the composition. Groups can form an association by a characteristic hydrogen bond described in detail later. Moreover, a hydrogen bond network can be formed also with the hydrogen bond group in the other component which comprises a polymeric composition.
Therefore, in the polymerizable composition of the present invention, it is possible to make each component constituting it close as desired. That is, by using a compound having a multipoint hydrogen-bonding group as described above for one or both of two essential components, the multipoint hydrogen-bonding groups, or the multipoint hydrogen-bonding group and another hydrogen Since a hydrogen bonding network is formed between the bonding groups, the two essential components can be present in the composition in close proximity. In addition, when using a compound having a multipoint hydrogen bonding group as an additive of an optional component, a hydrogen atom between the multipoint hydrogen bonding group and another hydrogen bonding group is present between the additive and the essential component. Since a binding network is formed, essential components can be present in close proximity via the additive. From these facts, it is presumed that in the polymerizable composition of the present invention, the polymerization reaction efficiency is improved, and as a result, excellent sensitivity and film strength can be obtained.

When such a polymerizable composition is applied to the photosensitive layer of a lithographic printing plate precursor, the multipoint hydrogen bond formed by the compound having a multipoint hydrogen bonding group is like a photosensitive layer (a coating film of the polymerizable composition). In the state where water does not intervene, it acts strongly, so that the sensitivity and printing durability can be improved corresponding to the film properties (sensitivity and film strength) as described above.
Such multi-point hydrogen bonds are non-covalent bonds, and in the situation where a protic medium such as water (for example, developer) is present, water molecules inhibit the formation of hydrogen bonds between functional groups. In general, hydrogen bond formation is impossible. From the above, in the exposed part of the photosensitive layer, the film density is improved by cross-linking and polymerization, so that the penetration of the developer into the film is reduced. On the other hand, in the unexposed part of the photosensitive layer, the crosslinking reaction or polymerization reaction does not occur, and the penetration of the developer into the film is not suppressed. It is presumed that the unexposed part of the photosensitive layer can be easily developed. As a result, it seems that a large number of good printed materials having no stain on the non-image area can be obtained.

  According to the present invention, it is possible to provide a polymerizable composition exhibiting excellent film strength and high sensitivity, and a lithographic printing plate precursor excellent in printing durability and sensitivity and suitable for drawing with a laser beam.

The present invention will be described below.
<Polymerizable composition>
The polymerizable composition of the present invention is a polymerizable composition containing a polymerizable compound, a binder polymer, a polymerization initiator, and a sensitizing dye, and at least one of the components constituting this is a non-shared electron pair. And a hydrogen atom capable of hydrogen bonding, and a compound having a substituent (multi-point hydrogen bonding group) capable of forming two or more hydrogen bonds.
That is, the polymerizable composition of the present invention is composed of four essential components and optional components of a binder polymer, a polymerizable compound, a polymerization initiator, and a sensitizing dye, and at least one of these components is It is necessary to be a compound having a multipoint hydrogen bonding group. For example, when none of the above four essential components is a compound having a multipoint hydrogen-bonding group, the polymerization property of the present invention can be obtained by containing an additive having a multipoint hydrogen-bonding group as an optional component. A composition is constructed.

  Since such a polymerizable composition of the present invention contains a sensitizing dye, when the sensitizing dye is exposed at a wavelength to which the sensitizing dye can respond, only the exposed part generates heat or sensitizes. . And the polymerization initiator generates radicals by the heat, and the polymerizable compound causes a polymerization reaction by the generated radicals. Since it has such a polymerization mechanism, in order to improve film strength and sensitivity, (1) a binder polymer having a multipoint hydrogen-bonding group, and (2) a polymerizability having a multipoint hydrogen-bonding group, which will be described later. A compound, (3) a polymerization initiator having a multipoint hydrogen bond group, (4) a sensitizing dye having a multipoint hydrogen bond group, and (5) an additive having a multipoint hydrogen bond group, Can be combined with two or more components.

In the polymerizable composition of the present invention, (1) a binder polymer having a multipoint hydrogen bonding group, (2) a polymerizable compound having a multipoint hydrogen bonding group, and (3) a multipoint hydrogen bonding group. A mode in which a polymerization initiator and (4) at least one component of a sensitizing dye having a multipoint hydrogen bonding group are used in combination is preferable. According to this aspect, in the composition, since a multipoint hydrogen bond is formed between the binder polymer component and the low molecular component, both components are present in close proximity. As a result, the polymerization described above is performed. This is because the efficiency of the mechanism is improved.
In particular, an embodiment in which (1) a binder polymer having a multipoint hydrogen bonding group and (2) a polymerizable compound having a multipoint hydrogen bonding group is used in combination. According to this aspect, in the composition, a multipoint hydrogen bond is formed between the binder polymer component and the polymerizable compound component, and the polymerizable compound is added around the binder polymer added to improve the film property. Will be polymerized and cured. In addition, since the polymerizable compositions are also close to each other, the polymerization efficiency is also improved. From these, the sensitivity and the film strength are further improved.

  Such a polymerizable composition of the present invention can be applied to various uses utilizing these mechanisms, for example, a photosensitive layer of a lithographic printing plate precursor that can be directly drawn by an infrared laser or the like, an image It is also suitable as a recording material or a high-sensitivity optical modeling material, and can be applied to a hologram material by utilizing a change in refractive index accompanying polymerization, or to an electronic material production such as a photoresist. Among these, it is particularly suitable as a photosensitive layer of a lithographic printing plate precursor that can be directly drawn by laser exposure or the like.

  First, the “substituent group (multi-point hydrogen bonding group) having an unshared electron pair and a hydrogen atom capable of hydrogen bonding and capable of forming two or more hydrogen bonds” in the present invention will be described.

[Multi-point hydrogen bonding group]
The multipoint hydrogen bonding group in the present invention is not particularly limited as long as it has a lone pair and a hydrogen atom capable of hydrogen bonding and can form two or more thermally reversible hydrogen bonds. Absent. That is, the multipoint hydrogen bonding group is an acceptor site (unshared electron pair) that accepts a hydrogen atom in one substituent and a donor site (hydrogen atom capable of hydrogen bonding) that supplies the acceptor site with a hydrogen atom. And two or more hydrogen bonds that are thermally reversible are not formed within one substituent, but are another specific substituent present in the membrane. Formed between.
Here, when the acceptor site is represented by “A” and the donor site is represented by “D”, the multipoint hydrogen bonding group according to the present invention has at least one partial structure represented by the following general formula (1). It is. Furthermore, the multipoint hydrogen-bonding group having such a partial structure forms characteristic hydrogen bonds that are alternately engaged as shown in the following reaction formula (1). The following reaction formula (1) is an example in which two thermally reversible hydrogen bonds are formed.

The multipoint hydrogen-bonding group is characterized in that it can form two or more such hydrogen bonds. In addition to improving the film strength and sensitivity, the multipoint hydrogen-bonding group balances developability and various performances. From the viewpoint of inclusion, those capable of forming three or more hydrogen bonds are preferable, and those capable of forming four or more hydrogen bonds are more preferable.
Here, if the interaction between the multipoint hydrogen bonding groups is expressed by a stabilization constant, it preferably has a stabilization constant greater than about 1 × 10 ² M ^{−1 and} greater than about 1 × 10 ³ M ^−1. It is more preferable to have a stabilization constant, and it is particularly preferable to have a stabilization constant greater than about 1 × 10 ⁴ M ⁻¹ .
In addition, since it is preferable that multipoint hydrogen bonding groups having the same structure form an interaction, from the viewpoint of forming a perfect pair between the acceptor site and the donor site, 2 or 4 hydrogen bonds are formed. A group capable of forming four hydrogen bonds is more preferable from the viewpoint of the strength of interaction.

The following general formula (2-1) represents a partial structure of a specific substituent capable of forming four hydrogen bonds, and the reaction formula (2-1) represents a partial structure represented by the general formula (2-1). This is an example in which the specific substituents having a hydrogen atom form four hydrogen bonds.
Similarly, the following general formula (2-2) represents a partial structure of a specific substituent capable of forming four hydrogen bonds, and the reaction formula (2-2) is represented by the general formula (2-2). This is an example in which the specific substituents having the partial structure form four hydrogen bonds.

  Here, as a specific example of the acceptor site A (unshared electron pair), an oxygen atom of a carbonyl group (> C═O), a sulfur atom of a thiocarbonyl group (> C═S), an enamine or a heterocyclic ring is formed. = N-, = P-, etc. are mentioned. Among them, from the viewpoint of forming a stronger hydrogen bond with a hydrogen atom, an oxygen atom and = N- are preferred.

  Specific examples of the donor site D (hydrogen atom capable of hydrogen bonding) include a hydrogen atom covalently bonded to a nitrogen atom, a hydrogen atom covalently bonded to an oxygen atom, and a hydrogen covalently bonded to a sulfur atom. In particular, from the viewpoint of forming a stronger hydrogen bond with the acceptor site, it is shared with a hydrogen atom or an oxygen atom that is covalently bonded to a nitrogen atom. A bonded hydrogen atom is preferred. However, when these hydrogen atoms are dissociated by the action of an aqueous alkali solution, the alkali resistance in the image area is lowered, so the pKa of the hydrogen atoms is preferably larger than 12.

A single bond may be directly bonded between the acceptor site and the donor site, between the two acceptor sites, or between the two donor sites, which are present in one multipoint hydrogen bonding group. From the viewpoint of reducing the influence of secondary interactions other than the primary interaction between the facing parts when forming an interaction with other multipoint hydrogen bonding groups, It is preferable that a divalent organic group having 1 atom or more is present between them. In particular, the connection between divalent organic groups via one atom is preferable so that the distance between each part does not become too long. As an example of a preferable linking group, a divalent organic group containing a carbon atom is preferable, and a linking group composed of sp ² carbons (-CO-, which is not involved in the formation of a ring structure) in order to keep the substituent conformation moderately. -CH = etc.) is mentioned as a preferred linking group.

Specific examples of such a multipoint hydrogen bonding group include those described in the following documents. For example, for a bifunctional compound in which an oligomer or polymer can be bonded by a two-point hydrogen bonding unit, J. Org. Org. Chem. 53, 5787-9 (1988). Supramolecular polymers based on 3-point hydrogen bonding units are disclosed in Macromolecules, 28, 782-83 (1995).
Representative compounds formed by bonding oligomers or polymers with a two-point hydrogen bonding unit include, for example, J. Org. Org. Chem. , 53, 5787-9 (1988), which is at least one alkali-soluble, such as a carboxylic acid group, a sulfonic acid, an imide, an N-acylsulfonamide, a phenolic hydroxyl group, and the like. Supplied by the system having a group.

  Among these, in the present invention, the multipoint hydrogen bonding group is most preferably a four point hydrogen bonding group represented by the following general formula (I).

In the general formula (I), R ¹ and R ² each independently represents a hydrogen atom or an organic group such as a hydrocarbyl group. R ¹ and R ² may be linked to form a cyclic structure.
Examples of the hydrocarbyl group represented by R ¹ and R ² include linear, branched, or cyclic alkyl groups, alkenyl groups, aryl groups, and aralkyl groups having 1 to 22 carbon atoms. These groups may further have a substituent, and examples of the substituent include a halogen atom, a hydroxy group, a hydrocarboxy group, a carboxy group, an ester group, a ketone group, a cyano group, an amino group, and an amide group. , And a nitro group.
The hydrocarbyl group in the present invention includes those containing an oxygen atom, a nitrogen atom, or a sulfur atom in the carbon chain in the hydrocarbyl group.

When R ¹ and R ² are linked to form a cyclic structure, R ¹ and R ² are preferably hydrocarbylene groups. Examples of the hydrocarbylene group include linear, branched, or cyclic alkylene groups having 1 to 22 carbon atoms, vinylene groups, arylene groups, aralkylene groups, and the like. These groups may further have a substituent, and examples of the substituent include a halogen atom, a hydroxy group, a carboxy group, a hydrocarboxy group, an ester group, a ketone group, a cyano group, an amino group, and an amide group. , And a nitro group.
Further, the hydrocarbylene group in the present invention includes those containing an oxygen atom, a nitrogen atom, or a sulfur atom in the carbon chain in the hydrocarbylene group.

[(1) Binder polymer having multipoint hydrogen bonding group]
In the present invention, the binder polymer having a multipoint hydrogen-bonding group may be one obtained by introducing a multipoint hydrogen-bonding group into the side chain of the binder polymer described later using a polymer reaction or a multipoint hydrogen-bonding group in advance. The monomer which has is prepared and this is copolymerized with another monomer is used.
In the present invention, the content of the multipoint hydrogen bonding group in the binder polymer having a multipoint hydrogen bonding group is preferably in the range of 0.01 to 10.0 mmol / g, more preferably 0.1 to 10.0 mmol / g. It is the range of 8.0 mmol / g, Most preferably, it is the range of 0.5-5.0 mmol / g.

The binder polymer into which a multipoint hydrogen bonding group can be introduced into the side chain is not particularly limited, but preferably has an alkali-soluble group such as a carboxy group from the viewpoint of the balance between sensitivity and developability. . For example, the polymers described in JP-B-54-34327, JP-B-58-12577, JP-A-60-159743, and JP-A-60-208748 are preferable. From the viewpoint of film strength, the polymers described in JP-A Nos. 2002-107918 and 2002-251008 are also preferable. Furthermore, from the viewpoint of satisfying all of film strength, sensitivity, and developability in a well-balanced manner, the polymer described in Japanese Patent Application No. 2003-339817 and the polymer described in Japanese Patent Application Laid-Open No. 2002-251008 are particularly preferable.
Moreover, as another monomer copolymerized with the monomer which has a multipoint hydrogen bonding group, the monomer used when synthesize | combining said polymer is mentioned.

  Specific examples of the binder polymer having a multipoint hydrogen bonding group in the present invention are shown below.

  The molecular weight of the binder polymer having a multipoint hydrogen-bonding group in the present invention is 2,000 to 1,000,000, more preferably 5,000 to 500,000, and still more preferably, from the viewpoint of image formability and film strength. Is in the range of 10,000 to 300,000.

  In addition, the binder polymer having a multipoint hydrogen bonding group in the present invention may be used alone or in combination of two or more, and further has a multipoint hydrogen bonding group. Other binder polymers that are not used may be used in combination. The other binder polymer is used in the range of 1 to 60% by mass, preferably 1 to 40% by mass, and more preferably 1 to 20% by mass with respect to the total mass of the binder polymer component. As the binder polymer that can be used in combination, a conventionally known binder polymer can be used without limitation, and specifically, an acrylic main chain binder, a urethane binder, or the like often used in the industry is preferably used.

The total amount of the binder polymer having a multipoint hydrogen bonding group and other binder polymer that may be used in combination can be determined as appropriate, but from the viewpoint of sensitivity and film strength, the non-volatile component in the polymerizable compound It is 10-90 mass% normally with respect to total mass, Preferably it is 20-80 mass%, More preferably, it is the range of 30-70 mass%.
In addition, when using the polymerizable composition of this invention for the photosensitive layer of a lithographic printing plate precursor, it is preferable that it is the same content.

[(2) Polymerizable compound having a multipoint hydrogen bonding group]
The polymerizable compound having a multipoint hydrogen-bonding group in the present invention is obtained by using, as a raw material, a part of the unsaturated group at the terminal of the polymerizable compound described later as a hydroxyl group, and the hydroxyl group is represented by the following general formula (II) Those modified with the compounds represented are preferably used.

In general formula (II), R ¹ and R ² each independently represents a hydrogen atom or an organic group such as a hydrocarbyl group. R ¹ and R ² may be linked to form a cyclic structure. Y is a hydrocarbylene group derived from a diisocyanate represented by Y ′ (NCO) ₂ .
R ¹ and R ² in the general formula (II) has the same meaning as R ¹ and R ² in the general formula (I), and preferred examples are also the same.

As the diisocyanate represented by Y ′ (NCO) ₂ , any diisocyanate can be used, and preferably, for example, isophorone diisocyanate, methylene-bis-phenyl diisocyanate, toluene isocyanate, hexamethylene diisocyanate, tetramethylxylylene. Examples include diisocyanates, dimers thereof, addition products of these with diols, and mixtures thereof.

  In the present invention, the polymerizable compound that can be a raw material for the polymerizable compound having a multipoint hydrogen bondable group is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and has at least an ethylenically unsaturated bond. It is selected from compounds having one, preferably two or more. Such a compound group is widely known in the industrial field, and can be used without any particular limitation in the present invention. These have chemical forms such as monomers, prepolymers, that is, dimers, trimers and oligomers, or mixtures thereof and copolymers thereof. Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester monomer of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound and an amide monomer of an unsaturated carboxylic acid and an aliphatic polyamine compound are used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, amino group or mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or In addition, 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, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

  Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate , Tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate , Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer.

  Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy- 2-hydroxypro ) Phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

  Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate. Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  Examples of other esters include aliphatic alcohol esters described in JP-B-46-27926, JP-B-51-47334, JP-A-57-196231, JP-A-59-5240, JP-A-59-5241. Those having an aromatic skeleton described in JP-A-2-226149 and those containing an amino group described in JP-A-1-165613 are also preferably used. Furthermore, the ester monomers described above can also be used as a mixture.

  Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like. Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B-54-21726.

  In addition, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable, and specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinyl urethane 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 formula (a) to a polyisocyanate compound having two or more isocyanate groups. Etc.

CH ₂ ═C (R ^a ) COOCH ₂ CH (R ^b ) OH Formula (a)
(However, R ^a and R ^b represent H or CH _3. )

  Also, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, JP-B-58-49860, JP-B-56-17654, Urethane compounds having an ethylene oxide skeleton described in JP-B-62-39417 and JP-B-62-39418 are also suitable. Further, by using addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238, It is possible to obtain a photopolymerizable composition excellent in the photosensitive speed.

  Other examples include polyester acrylates, epoxy resins and (meth) acrylic acid as described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, and JP-A-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as reacted epoxy acrylates. Further, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337 and JP-B-1-40336, vinylphosphonic acid compounds described in JP-A-2-25493, and the like can also be mentioned. . In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

  Hereinafter, specific examples of the polymerizable compound having a multipoint hydrogen bonding group synthesized using these polymerizable compounds as raw materials are shown below.

These polymerizable compounds having a multipoint hydrogen-bonding group may be used alone or in combination of two or more, and used in combination with other polymerizable compounds that do not have a multipoint hydrogen-bonding group. May be. The other polymerizable compound is used in the range of 1 to 60% by mass, preferably 1 to 40% by mass, and more preferably 1 to 20% by mass with respect to the total mass of the polymerizable compound component. In addition, as the other polymerizable compounds, conventionally known compounds can be used without limitation, specifically, the polymerizable compounds listed above, which are used as a raw material for the polymerizable compound having a multipoint hydrogen bonding group. Is preferably used.
The total content of the polymerizable compound components including the polymerizable compound having a multipoint hydrogen bonding group is preferably 5 to 80 with respect to the nonvolatile components in the polymerizable composition from the viewpoint of sensitivity and film strength. It is in the range of 25% by mass, more preferably 25% by mass.

  In addition, when the polymerizable composition of the present invention is applied to the photosensitive layer of a lithographic printing plate precursor, the structure of the polymerizable compound having a multipoint hydrogen bonding group, whether it is used alone or in combination, how to use it, etc. The details of can be arbitrarily set according to the performance design of the final lithographic printing plate precursor. For example, it is selected from the following viewpoints. From the viewpoint of photosensitive speed, a structure having a high unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, in order to increase the strength of the image area, that is, the cured film, those having three or more functionalities are preferable, and furthermore, different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether). It is also effective to adjust both photosensitivity and strength by using a compound of the type). A compound having a large molecular weight or a compound having high hydrophobicity is excellent in photosensitive speed and film strength, but is not preferable in terms of development speed and precipitation in a developer. In addition, the selection and use method of the addition polymerization compound is also an important factor for the compatibility and dispersibility with other components in the photosensitive layer (for example, binder polymer, initiator, colorant, etc.). In some cases, the compatibility can be improved by using a low-purity compound or by using two or more kinds in combination. In addition, a specific structure may be selected for the purpose of improving the adhesion of the support or the overcoat layer described later. These may be used alone or in combination of two or more. In addition, the use method of the addition polymerizable compound can be arbitrarily selected from the viewpoint of polymerization inhibition with respect to oxygen, resolution, fogging property, refractive index change, surface adhesiveness, etc. Depending on the case, a layer configuration and coating method such as undercoating and overcoating can be performed.

[(3) Polymerization initiator having a multipoint hydrogen bonding group]
As the polymerization initiator having a multipoint hydrogen bonding group in the present invention, a polymerization initiator having a multipoint hydrogen bonding group introduced into the structure of the polymerization initiator described later is used.
Polymerization initiators capable of introducing a multipoint hydrogen bonding group include (a) aromatic ketones, (b) aromatic onium salt compounds, (c) organic peroxides, (d) thio compounds, (e) Hexaarylbiimidazole compounds, (f) ketoxime ester compounds, (g) borate compounds, (h) azinium compounds, (i) metallocene compounds, (j) active ester compounds, (k) compounds having a carbon halogen bond, etc. Can be mentioned. Specific examples of the above (a) to (k) are given below, but the present invention is not limited to these.

(A) Aromatic ketones (a) Aromatic ketones preferred as the polymerization initiator used in the present invention include "RADIATION CURING IN POLYMER SCIENCE AND TECHNOLOGY" P. FouassIer, J. et al. F. Examples include compounds having a benzophenone skeleton or a thioxanthone skeleton described in Rabek (1993), p77-117. For example, the following compounds are mentioned.

  Among them, examples of particularly preferred (a) aromatic ketones include α-thiobenzophenone compounds described in JP-B-47-6416, benzoin ether compounds described in JP-B-47-3981, for example, the following compounds.

  Examples of the α-substituted benzoin compounds described in JP-B-47-22326 include the following compounds.

  Examples thereof include benzoin derivatives described in JP-B-47-23664, aroylphosphonic acid esters described in JP-A-57-30704, dialkoxybenzophenones described in JP-B-60-26483, for example, the following compounds.

  Examples of the benzoin ethers described in JP-B-60-26403 and JP-A-62-181345 include the following compounds.

  Examples of the α-aminobenzophenones described in JP-B-1-34242, US Pat. No. 4,318,791, and European Patent 0284561A1, such as the following compounds.

  P-Di (dimethylaminobenzoyl) benzene described in JP-A-2-211452, for example, the following compounds may be mentioned.

  Examples of the thio-substituted aromatic ketone described in JP-A-61-194062 include the following compounds.

  The acylphosphine sulfide described in JP-B-2-9597, for example, the following compounds may be mentioned.

  Examples of the acylphosphine described in JP-B-2-9596 include the following compounds.

  Further, thioxanthones described in JP-B-63-61950, coumarins described in JP-B-59-42864, and the like can also be mentioned.

(B) Onium Salt Compound As the polymerization initiator (b) preferable as the polymerization initiator used in the present invention, compounds represented by the following general formulas (1) to (3) may be mentioned.

In general formula (1), Ar ¹ and Ar ² each independently represent an aryl group having 20 or less carbon atoms, which may have a substituent. Preferred substituents when this aryl group has a substituent include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, or a carbon atom having 12 or less carbon atoms. An aryloxy group is mentioned. (Z ² ) ⁻ represents a counter ion selected from the group consisting of halogen ion, perchlorate ion, carboxylate ion, tetrafluoroborate ion, hexafluorophosphate ion, and sulfonate ion, preferably perchloric acid Ions, hexafluorophosphate ions, and aryl sulfonate ions.

In General Formula (2), Ar ³ represents an aryl group having 20 or less carbon atoms, which may have a substituent. Preferred examples of the substituent include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, an aryloxy group having 12 or less carbon atoms, and 12 or less carbon atoms. Examples thereof include an alkylamino group, a dialkylamino group having 12 or less carbon atoms, an arylamino group having 12 or less carbon atoms, or a diarylamino group having 12 or less carbon atoms. (Z ³ ) ⁻ represents a counter ion having the same meaning as (Z ² ) ⁻ .

In general formula (3), R ²³ , R ²⁴ and R ²⁵ may be the same or different and each represents a hydrocarbon group having 20 or less carbon atoms which may have a substituent. Preferable substituents include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, or an aryloxy group having 12 or less carbon atoms. (Z ⁴ ) ⁻ represents a counter ion having the same meaning as (Z ² ) ⁻ .

In the present invention, specific examples of the onium salt compound that can be suitably used as the polymerization initiator include those described in JP-A No. 2001-133696.
In the present invention, the onium salt compounds represented by the general formula (1) ([OI-1] to [OI-10]) and the onium salt compounds represented by the general formula (2) (which can be suitably used in the present invention) Specific examples of [ON-1] to [ON-5]) and the onium salt compounds represented by the general formula (3) ([OS-1] to [OS-7]) will be given, but the present invention is not limited thereto. It is not a thing.

  The onium salt used in the present invention preferably has a maximum absorption wavelength of 400 nm or less, and more preferably 360 nm or less. Thus, when the polymerizable composition of the present invention is applied to the recording layer of the lithographic printing plate precursor, the lithographic printing plate precursor can be handled under white light by setting the absorption wavelength in the ultraviolet region. it can.

(C) Organic peroxide Preferred as the polymerization initiator used in the present invention (c) Organic peroxide includes almost all organic compounds having one or more oxygen-oxygen bonds in the molecule. Examples include methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (tertiarybutylperoxy) -3,3,5. -Trimethylcyclohexane, 1,1-bis (tertiarybutylperoxy) cyclohexane, 2,2-bis (tertiarybutylperoxy) butane, tertiarybutylhydroperoxide, cumene hydroperoxide, diisopropylbenzenehydride Loperoxide, parameter hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, ditertiary butyl peroxide, tertiary butyl Cumyl peroxide, dicumyl peroxide, bis (tertiarybutylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (tertiarybutylperoxy) hexane, 2,5-xanoyl peroxide, peroxy Succinic oxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, meta-toluoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate Nate, dimethoxyisopropyl peroxycarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, tertiary butyl peroxyacetate, tertiary butyl peroxypivalate, tertiary butyl peroxyneodecanoate, tarsha Tributyl peroxyoctanoate, tertiary butyl peroxy-3,5,5-trimethylhexanoate, tertiary butyl peroxylaurate, tertiary carbonate, 3,3'4,4'-tetra- (t -Butylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (t-amylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (t-hexylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (T-octylperoxycarbonyl) benzophenone, 3,3′4,4′-tetra- (cumylperoxycarbonyl) benzophenone, 3,3′4,4′-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone Carbonyldi (t-butylperoxydihydrogen diphthalate), carbonyldi (t-hexylperoxydihydrogen diphthalate), and the like.

  Among them, 3,3′4,4′-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3′4,4′-tetra- (t-amylperoxycarbonyl) benzophenone, 3,3′4 4'-tetra- (t-hexylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (t-octylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (cumylper) Peroxyesters such as (oxycarbonyl) benzophenone, 3,3′4,4′-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone, di-t-butyldiperoxyisophthalate are preferred.

(D) Thio compound As a preferable (d) thio compound as a polymerization initiator used by this invention, the compound which has a structure shown by following General formula (4) is mentioned.

In the general formula (4), R ²⁶ represents an alkyl group, an aryl group or a substituted aryl group, and R ²⁷ represents a hydrogen atom or an alkyl group. R ²⁶ and R ²⁷ represent a group of nonmetallic atoms necessary to form a 5-membered to 7-membered ring which may be bonded to each other and contain a hetero atom selected from oxygen, sulfur and nitrogen atoms.

As an alkyl group in the said General formula (4), a C1-C4 thing is preferable. The aryl group is preferably one having 6 to 10 carbon atoms such as phenyl or naphthyl, and the substituted aryl group may be a halogen atom such as a chlorine atom or a methyl group as described above. Those substituted with an alkoxy group such as an alkyl group, a methoxy group, and an ethoxy group are included. R ²⁷ is preferably an alkyl group having 1 to 4 carbon atoms.
Specific examples of the thio compound represented by the general formula (4) include compounds as shown in Table 1 below.

(E) Hexaarylbiimidazole compound (e) Hexaarylbiimidazole compounds preferred as the polymerization initiator used in the present invention include lophine dimers described in JP-B Nos. 45-37377 and 44-86516, such as 2 , 2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-bromophenyl) -4,4 ′, 5,5′-tetra Phenylbiimidazole, 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′-tetra Examples thereof include phenylbiimidazole and 2,2′-bis (o-trifluorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole.

(F) Ketooxime ester compound (f) The ketoxime ester compound preferable as a polymerization initiator used in the present invention includes 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutane-2-one, 3 -Propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, Examples include 3-p-toluenesulfonyloxyiminobutan-2-one and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.

(G) Borate Compound As an example of the (g) borate compound preferable as the polymerization initiator used in the present invention, a compound represented by the following general formula (5) can be given.

In the general formula (5), R ²⁸ , R ²⁹ , R ³⁰ and R ³¹ may be the same or different from each other, and each is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted group. An alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted heterocyclic group, wherein R ²⁸ , R ²⁹ , R ³⁰ and R ³¹ are bonded to form a cyclic structure. May be. However, at least one of R ²⁸ , R ²⁹ , R ³⁰ and R ³¹ is a substituted or unsubstituted alkyl group. (Z ⁵ ) ⁺ represents an alkali metal cation or a quaternary ammonium cation.

Examples of the alkyl group for R ^{28 to} R ³¹ include straight-chain, branched, and cyclic groups, and those having 1 to 18 carbon atoms are preferable. Specifically, methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, octyl, stearyl, cyclobutyl, cyclopentyl, cyclohexyl and the like are included. The substituted alkyl group includes an alkyl group as described above, a halogen atom (for example, —Cl, —Br, etc.), a cyano group, a nitro group, an aryl group (preferably a phenyl group), a hydroxy group, —COOR ³² (here R ³² represents a hydrogen atom, an alkyl group having 1 to 14 carbon atoms, or an aryl group), —OCOR ³³ or —OR ³⁴ (where R ³³ and R ³⁴ are alkyl groups having 1 to 14 carbon atoms, or aryl. And a group having a substituent represented by the following formula.

(Wherein R ³⁵ and R ³⁶ independently represent a hydrogen atom, an alkyl group having 1 to 14 carbon atoms, or an aryl group)

The aryl group of R ^{28 to} R ³¹ includes 1 to 3 ring aryl groups such as a phenyl group and a naphthyl group, and the substituted aryl group is a substitution of the above substituted alkyl group with the above aryl group. Those having a group or an alkyl group having 1 to 14 carbon atoms are included. Examples of the alkenyl group for R ^{28 to} R ³¹ include linear, branched and cyclic groups having 2 to 18 carbon atoms. Examples of the substituent of the substituted alkenyl group include those listed as the substituents of the substituted alkyl group. Examples of the alkynyl group of R ^{28 to} R ³¹ include straight chain or branched groups having 2 to 28 carbon atoms, and examples of the substituent of the substituted alkynyl group include those listed as the substituents of the substituted alkyl group. included. In addition, examples of the heterocyclic group of R ^{28 to} R ³¹ include a 5-membered ring or more, preferably a 5- to 7-membered heterocyclic group containing at least one of N, S, and O. May contain a condensed ring. Furthermore, you may have what was mentioned as a substituent of the above-mentioned substituted aryl group as a substituent. Specific examples of the compound represented by the general formula (5) are described in US Pat. Nos. 3,567,453 and 4,343,891, European Patents 109,772 and 109,773. Compounds and those shown below are mentioned.

(H) Azinium Compound Preferred examples of the azinium salt compound used as the polymerization initiator used in the present invention include JP-A Nos. 63-138345, 63-142345, 63-142346 and 63-142346. Examples thereof include compounds having an N—O bond described in JP-A-63-143537 and JP-B-46-42363.

(I) Metallocene compound (i) Metallocene compounds preferred as the polymerization initiator used in the present invention include those disclosed in JP-A Nos. 59-152396, 61-151197, 63-41484, and JP-A-2. And titanocene compounds described in JP-A No.-249 and JP-A-2-4705, and iron-arene complexes described in JP-A-1-304453 and JP-A-1-152109.

  Specific examples of the titanocene compound include di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, and di-cyclopentadienyl-Ti-bis-2,3. 4,5,6-pentafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti- Bis-2,4,6-trifluorophen-1-yl, di-cyclopentadienyl-Ti-2,6-difluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4 -Difluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, di-methylcyclopentadienyl-Ti- -2,3,5,6-tetrafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4-difluorophen-1-yl, bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyridin-1-yl) phenyl) titanium bis (cyclopentadienyl) bis [2,6-difluoro-3- (methylsulfonamido) phenyl] titanium, bis (cyclopentadi Enyl) bis [2,6-difluoro-3- (N-butylbialoyl-amino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-butyl- (4-chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3 -(N-benzyl-2,2-dimethylpentanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (2-ethylhexyl) -4-tolyl-sulfonyl] ) Amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3-oxaheptyl) benzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2 , 6-Difluoro-3- (N- (3,6-dioxadecyl) benzoylamino) phenyl] titanium, bis (cyclopentadienyl) bi [2,6-difluoro-3- (trifluoromethylsulfonyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (trifluoroacetyl) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3- (2-chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (4-chloro Benzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3,6-dioxadecyl) -2,2-dimethylpentanoylamino) phenyl] titanium, bis (Cyclopentadienyl) bis [2,6-difluoro-3- (N- (3,7-dimethyl-7-methoxyoctyl) benzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 -Difluoro-3- (N-cyclohexylbenzoylamino) phenyl] titanium and the like.

(J) Active ester compound Preferred as a polymerization initiator used in the present invention (j) As an active ester compound, imide sulfonate compounds described in JP-B-62-2223, JP-B-63-14340, JP-A-59-174831 Mention may be made of the active sulfonates described.

(K) Compound Having Carbon Halogen Bond Preferred examples of the compound (k) having a carbon halogen bond as the polymerization initiator used in the present invention include compounds represented by the following general formulas (6) to (12). .

In the general formula (6), X ² represents a halogen atom, and Y ¹ represents —C (X ² ) ₃ , —NH ₂ , —NHR ³⁸ , —NR ³⁸ , —OR ³⁸ . Here, R ³⁸ represents an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group. R ³⁷ represents —C (X ² ) ₃ , an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or a substituted alkenyl group.

In the general formula (7), R ³⁹ is an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group, a substituted aryl group, a halogen atom, an alkoxy group, a substituted alkoxyl group, a nitro group or a cyano group, and X ³ is a halogen atom, and n is an integer of 1 to 3.

In the general formula (8), R ⁴⁰ is an aryl group or a substituted aryl group, R ⁴¹ is a group or halogen shown below, and Z ⁶ is —C (═O) —, —C (═S) — or —SO ₂ —, X ³ is a halogen atom, and m is 1 or 2.

R ⁴² and R ⁴³ are an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group or a substituted aryl group, and R ⁴⁴ is the same as R ³⁸ in the general formula (6).

In the general formula (9), R ⁴⁵ is an optionally substituted aryl group or heterocyclic group, R ⁴⁶ is a trihaloalkyl group or trihaloalkenyl group having 1 to 3 carbon atoms, and p is 1 2 or 3.

The compound represented by the general formula (10) represents a carbonylmethylene heterocyclic compound having a trihalogenomethyl group.
In the general formula (10), L ⁷ is a hydrogen atom or a substituent of the formula: CO— (R ⁴⁷ ) q (C (X ⁴ ) ₃ ) r, Q ² is sulfur, selenium or oxygen atom, dialkylmethylene group Alkene-1,2-ylene group, 1,2-phenylene group or —N—R— group, and M ⁴ is a substituted or unsubstituted alkylene group or alkenylene group, or 1,2-arylene group R ⁴⁸ is an alkyl group, an aralkyl group or an alkoxyalkyl group, R ⁴⁷ is a carbocyclic or heterocyclic divalent aromatic group, and X ⁴ is a chlorine, bromine or iodine atom , Q = 0 and r = 1, or q = 1 and r = 1 or 2.

The compound represented by the general formula (11) represents a 4-halogeno-5- (halogenomethyl-phenyl) -oxazole derivative.
In general formula (11), X ⁵ is a halogen atom, t is an integer of 1 to 3, s is an integer of 1 to 4, and R ⁴⁹ is a hydrogen atom or a CH _3−t X ⁵ _t group. And R ⁵⁰ is an s-valent unsaturated organic group which may be substituted.

The compound represented by the general formula (12) represents a 2- (halogenomethyl-phenyl) -4-halogeno-oxazole derivative.
In the general formula (12), X ⁶ is a halogen atom, v is an integer of 1 to 3, u is an integer of 1 to 4, and R ⁵¹ is a hydrogen atom or a CH _3-v X ⁶ _v group. And R ⁵² represents an u-valent unsaturated organic group which may be substituted.

  Specific examples of such a compound having a carbon-halogen bond include, for example, Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), for example, 2-phenyl 4,6-bis (trichloromethyl) -S-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl)- S-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -S-triazine, 2 -(2 ', 4'-dichlorophenyl) -4,6-bis (trichloromethyl) -S-triazine, 2,4,6-tris (trichloromethyl) -S-triazine, 2-methyl-4,6 -Bis (trichloromethyl) -S-triazine, 2-n-nonyl-4,6-bis (trichloromethyl) -S-triazine, 2- (α, α, β-trichloroethyl) -4,6- Scan (trichloromethyl) -S- triazine. In addition, compounds described in British Patent 1388492, for example, 2-styryl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-methylstyryl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl) -4-amino-6-trichloromethyl-S-triazine, etc. And compounds described in JP-A No. 53-133428, such as 2- (4-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- (4-ethoxy-naphtho) 1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl] -4,6-bis-trichloro Til-S-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine), 2- (acenaphtho-5-yl) -4,6- Examples include compounds described in German Patent No. 3333724, such as bis-trichloromethyl-S-triazine, and the like.

  F.F. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), for example, 2-methyl-4,6-bis (tribromomethyl) -S-triazine, 2,4,6-tris (tribromomethyl) -S-triazine, 2, 4,6-tris (dibromomethyl) -S-triazine, 2-amino-4-methyl-6-tribromomethyl-S-triazine, 2-methoxy-4-methyl-6-trichloromethyl-S-triazine, etc. be able to. Furthermore, for example, the following compounds described in JP-A-62-258241 can be exemplified.

  In addition, for example, the following compounds described in JP-A-5-281728 can be exemplified.

  Alternatively, M.M. P. Hutt, E .; F. Elslager and L. M.M. The following compounds that can be easily synthesized by those skilled in the art according to the synthesis method described in “Journalof Heterocyclic Ic chemIstry”, Volume 7 (No. 3), page 511 et seq. (1970) by Herbel. Examples of the group include the following compounds.

  Still more preferred examples of the polymerization initiator in the present invention include the above-mentioned (a) aromatic ketones, (b) onium salt compounds, (c) organic peroxides, (e) hexaarylbiimidazole compounds, (i) ) Metallocene compounds, (k) compounds having a carbon halogen bond, and most preferred examples include aromatic iodonium salts, aromatic sulfonium salts, titanocene compounds, and trihalomethyls represented by general formula (6). -S-triazine compounds can be mentioned.

  Moreover, the oxime ester compound which can be used suitably as a polymerization initiator in this invention is demonstrated below. Preferred oxime ester compounds include the following general formula (i).

  In general formula (i), X represents a carbonyl group, a sulfone group, or a sulfoxide group, and Y represents a cyclic or chain alkyl group having 1 to 12 carbon atoms, an alkenyl group, an alkynyl group, or an aryl group having 6 to 18 carbon atoms. An aryl group is an aromatic hydrocarbon compound such as a benzene ring, naphthalene ring, anthracene ring, phenanthrene group, pyrene group, triphenylene group, and a heterocyclic ring is a nitrogen atom, sulfur atom, oxygen atom For example, a pyrrole group, a furan group, a thiophene group, a selenophenone group, a pyrazole group, an imidazole group, a triazole group, a tetrazole group, an oxazole group, a thiazole group, an indole group, Benzofuran group, benzimidazole group, benzoxazole group, benzothiazole group, pyridine group, Rimijin group, a pyrazine group, a triazine group, a quinoline group, a carbazole group, an acridine group, a phenoxazine, and a compound such as phenothiazine. These substituents represented by Y are halogen atoms, hydroxyl groups, nitrile groups, nitro groups, carboxyl groups, aldehyde groups, alkyl groups, thiol groups, aryl groups or alkenyl groups, alkynyl groups, ether groups, ester groups, ureas. Group, amino group, amide group, sulfide group, disulfide group, sulfoxide group, sulfo group, sulfone group, hydrazine group, carbonyl group, imino group, halogen atom, hydroxyl group, nitrile group, nitro group, carboxyl group, carbonyl group, urethane It can be substituted by a compound containing a group, an alkyl group, a thiol group, an aryl group, a phosphoroso group, a phospho group, or a carbonyl ether group.

  Z in the general formula (i) is synonymous with Y or is a nitrile group, a halogen atom, a hydrogen atom or an amino group, and these Z compounds are a halogen atom, a hydroxyl group, a nitrile group, a nitro group, a carboxyl group, an aldehyde group. , Alkyl group, thiol group, aryl group or alkenyl group, alkynyl group, ether group, ester group, urea group, amino group, amide group, sulfide group, disulfide group, sulfoxide group, sulfo group, sulfone group, hydrazine group, carbonyl Substitutable with compounds containing groups, imino groups, halogen atoms, hydroxyl groups, nitrile groups, nitro groups, carboxyl groups, carbonyl groups, urethane groups, alkyl groups, thiol groups, aryl groups, phosphoroso groups, phospho groups, carbonyl ether groups It is.

  W in the general formula (i) represents a divalent organic group, and represents a methylene group, a carbonyl group, a sulfoxide group, a sulfone group, or an imino group. The methylene group and imino group are an alkyl group, an aryl group, an ester group, and a nitrile. It can be substituted by a compound containing a group, a carbonyl ether group, a sulfo group, a sulfo ether group, an ether group or the like. n represents an integer of 0 or 1.

V in the general formula (i) is a cyclic or chain alkyl group having 1 to 12 carbon atoms, an alkenyl group, an alkynyl group, an aryl group having 6 to 18 carbon atoms, an alkoxy group, or an aryloxy group. Aromatic hydrocarbon compounds such as benzene ring, naphthalene ring, anthracene ring, phenanthrene group, pyrene group, triphenylene group, pyrrole group, furan group, thiophene group, selenophene group, pyrazole group, imidazole group, triazole group, tetrazole group, oxazole Group, thiazole group, indole group, benzofuran group, benzimidazole group, benzoxazole group, benzothiazole group, pyridine group, pyrimidine group, pyrazine group, triazine group, quinoline group, carbazole group, acridine group, phenoxazine, phenothiazine, etc. Heteroatom containing Aromatic compounds and the like. These V compounds are halogen atoms, hydroxyl groups, nitrile groups, nitro groups, carboxyl groups, aldehyde groups, alkyl groups, thiol groups, aryl groups or alkenyl groups, alkynyl groups, ether groups, ester groups, urea groups, amino groups, amides. Group, sulfide group, disulfide group, sulfoxide group, sulfo group, sulfone group, hydrazine group, carbonyl group, imino group, halogen atom, hydroxyl group, nitrile group, nitro group, carboxyl group, carbonyl group, urethane group, alkyl group, thiol It can be substituted by a compound containing a group, an aryl group, a phosphoroso group, a phospho group or a carbonyl ether group.
V and Z may be bonded to each other to form a ring.

As the oxime ester compound represented by the general formula (i), from the viewpoint of sensitivity, X is carbonyl, Y is an aryl group or benzoyl group, Z group is an alkyl group or aryl group, W is a carbonyl group, V Is preferably an aryl group. More preferably, the aryl group of V has a thioether substituent.
Note that the structure of the N—O bond in the general formula (i) may be E-form or Z-form.

  Other oxime ester compounds that can be suitably used in the present invention include Progress in Organic Coatings, 13 (1985) 123-150; C. S Perkin II (1979) 1653-1660; Journal of Photopolymer Science and Technology (1995) 205-232; C. S Perkin II (1979) 156-162; JP-A 2000-66385; JP-A 2000-80068.

  Although the specific example of the oxime ester compound which can be used suitably for this invention is shown below, it is not limited to this.

  Hereinafter, specific examples of the polymerization initiator having a multipoint hydrogen-bonding group in the present invention obtained by introducing a multipoint hydrogen-bonding group into these polymerization initiators are shown below.

  In the present invention, the polymerization initiator having a multipoint hydrogen bonding group may be used alone or in combination of two or more, and further has no multipoint hydrogen bonding group. Other polymerization initiators may be used in combination. The other polymerization initiator is used in the range of 1 to 80% by mass, preferably 1 to 60% by mass, and more preferably 1 to 40% by mass with respect to the total mass of the polymerization initiator component. As the other polymerization initiators, conventionally known polymerization initiators can be used without limitation, and specifically, the polymerization initiators listed above into which a multipoint hydrogen bonding group is introduced are preferably used.

  The polymerization initiator having a multipoint hydrogen bonding group is 0.1 to 50% by mass, preferably 0.5%, based on the total solid content constituting the polymerizable composition of the present invention, from the viewpoint of sensitivity and film strength. It can be added at a ratio of ˜30 mass%, particularly preferably 1 to 20 mass%.

  The polymerization initiator having a multipoint hydrogen bonding group may be added directly to the polymerizable composition together with other components, but it is the same even if another layer adjacent to this is provided and added thereto. The effect of can be obtained. In particular, when the polymerizable composition of the present invention is used in the photosensitive layer of a lithographic printing plate precursor described later, it may be added to the same layer as the image photosensitive layer, but another layer adjacent to this may be provided. Even if it is added thereto, the same effect can be obtained. Further, when the polymerizable composition of the present invention is used for the photosensitive layer of a lithographic printing plate precursor, the same content is preferable.

[(4) Sensitizing dye having a multipoint hydrogen bonding group]
As the sensitizing dye having a multipoint hydrogen bonding group in the present invention, a sensitizing dye having a multipoint hydrogen bonding group introduced in the structure of the sensitizing dye described later is used.
Examples of the sensitizing dye into which a multipoint hydrogen bonding group can be introduced include known spectral sensitizing dyes, or dyes or pigments that absorb light and interact with a polymerization initiator.

(Spectral sensitizing dye or dye)
Spectral sensitizing dyes or dyes used as sensitizing dyes into which a multipoint hydrogen bonding group can be introduced include polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein, eosin, erythrosine). , Rhodamine B, rose bengal), cyanines (eg thiacarbocyanine, oxacarbocyanine), merocyanines (eg merocyanine, carbomerocyanine), thiazines (eg thionine, methylene blue, toluidine blue), acridines (eg , Acridine orange, chloroflavin, acriflavine), phthalocyanines (eg, phthalocyanine, metal phthalocyanine), porphyrins (eg, tetraphenylporphyrin, central metal-substituted porphyrin), chlorophylls (eg, Chlorophyll, chlorophyllin, center metal-substituted chlorophyll), metal complexes (for example, the following compound), anthraquinones, such as (anthraquinone), squaryliums, for example (squarylium), and the like.

The example of a more preferable spectral sensitizing dye or dye is illustrated below.
A styryl dye described in JP-B-37-13034; a cationic dye described in JP-A-62-143044; a quinoxalinium salt described in JP-B-59-24147; described in JP-A-64-33104 A new methylene blue compound; anthraquinones described in JP-A No. 64-56767; benzoxanthene dyes described in JP-A No. 2-1714; acridines described in JP-A Nos. 2-226148 and 2-226149 Pyryllium salts described in JP-B-40-28499; Cyanines described in JP-B-46-42363; Benzofuran dyes described in JP-A-2-63053; JP-A-2-85858, JP-A-2-216154 Conjugated ketone dyes disclosed in Japanese Patent Publication No. 57-10605; Azocinnamylidene derivatives described in Japanese Patent No. 0321; cyanine dyes described in Japanese Patent Laid-Open No. 1-287105; Japanese Patent Laid-Open Nos. 62-31844, 62-31848, 62-1443043 Xanthene dyes described above; aminostyryl ketone described in JP-B-59-28325; dye described in JP-A-2-17943; merocyanine dye described in JP-A-2-244050; described in JP-B-59-28326 Merocyanine dyes described in JP-A-59-89303; merocyanine dyes described in Japanese Patent Application No. 6-269047; and benzopyran dyes described in Japanese Patent Application No. 7-16483.

  Further, compounds represented by the following general formula (III) are also suitable as sensitizing dyes.

In the general formula (III), R ⁶⁶ represents an aromatic ring or a hetero ring which may have a substituent, and A ⁵ represents an oxygen atom, a sulfur atom, or —NR ⁶⁷ —. R ⁶⁴ , R ⁶⁵ and R ⁶⁷ each independently represents a hydrogen atom or a monovalent nonmetallic atomic group, and R ⁶⁷ and R ⁶⁴ , R ⁶⁵ and R ⁶⁷ each represent an aliphatic or aromatic ring. Can be combined to form.
Hereinafter, preferable examples of the compound represented by the general formula (III) will be given.

(Infrared absorber)
An infrared absorber is also used as a sensitizing dye into which a multipoint hydrogen bonding group can be introduced. As the infrared absorber, the following dyes or pigments are suitable.
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, etc. Is mentioned.
Preferred dyes include, for example, cyanine dyes described in JP-A-58-125246, JP-A-59-84356, JP-A-59-202829, JP-A-60-78787, and the like. Methine dyes described in JP-A-58-173696, JP-A-58-181690, JP-A-58-194595, JP-A-58-112793, JP-A-58-224793, JP-A-59- 48187, JP-A-59-73996, JP-A-60-52940, JP-A-60-63744, etc., naphthoquinone dyes, JP-A-58-112792, etc. And cyanine dyes described in British Patent 434,875.

Also, a near infrared absorption sensitizer described in US Pat. No. 5,156,938 is preferably used, and a substituted arylbenzo (thio) pyrylium salt described in US Pat. No. 3,881,924, Trimethine thiapyrylium salts described in JP-A-57-142645 (US Pat. No. 4,327,169), JP-A-58-181051, 58-220143, 59-41363, 59-84248 Nos. 59-84249, 59-146063, 59-146061, pyranlium compounds, cyanine dyes described in JP-A-59-216146, US Pat. No. 4,283,475 The pentamethine thiopyrylium salts described above and the pyrylium compounds disclosed in Japanese Patent Publication Nos. 5-13514 and 5-19702 are also preferably used. . Another example of a preferable dye is a near-infrared absorbing dye described in US Pat. No. 4,756,993 as formulas (I) and (II).
Other preferable examples of the infrared absorbing dye in the present invention include specific indolenine cyanine dyes described in Japanese Patent Application Nos. 2001-6326 and 2001-237840 as exemplified below.

  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 formula (a), X ¹ represents a hydrogen atom, a halogen atom, -NPh _2, X ² -L ¹ or a group shown below. Here, X ² represents an oxygen atom, a nitrogen atom, or a sulfur atom, and L ¹ represents a hydrocarbon group having 1 to 12 carbon atoms, an aromatic ring having a hetero atom, or 1 to 1 carbon atom containing a hetero atom. 12 hydrocarbon groups are shown. Here, the hetero atom represents N, S, O, a halogen atom, or Se. Xa ^- the Za described later ^- is defined as for, R ^a represents a hydrogen atom, an alkyl group, an aryl group, a substituted or unsubstituted amino group, substituted or unsubstituted amino group and a halogen atom.

R ¹ and R ² each independently represents a hydrocarbon group having 1 to 12 carbon atoms. From the storage stability of the composition coating solution, R ¹ and R ² are preferably hydrocarbon groups having 2 or more carbon atoms, and R ¹ and R ² are bonded to each other to form a 5-membered ring or It is particularly preferable that a 6-membered ring is formed.

Ar ¹ and Ar ² may be the same or different and each represents an aromatic hydrocarbon group which may have a substituent. Preferred aromatic hydrocarbon 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 salt, in view of the storage stability of the composition coating solution. Fluorophosphate ions and aryl sulfonate ions.

  Specific examples of the cyanine dye represented by formula (a) that can be suitably used in the present invention include paragraph numbers [0017] to [0019] of JP-A No. 2001-133969 and JP-A No. 2002-40638. Mention may be made of the paragraph numbers [0012] to [0038] of the publication and the paragraph numbers [0012] to [0023] of JP 2002-23360 A.

  Examples of infrared absorbing pigments used as sensitizing dyes in the present invention include commercially available pigments and Color Index (CI) Handbook, “Latest Pigment Handbook” (edited by Japan Pigment Technical Association, published in 1977), “Latest Pigment Application”. The pigments described in “Technology” (CMC Publishing, 1986) and “Printing Ink Technology” CMC Publishing, 1984) can be used.

  Examples of the pigment include black pigments, yellow pigments, orange pigments, brown pigments, red pigments, purple pigments, blue pigments, green pigments, fluorescent pigments, metal powder pigments, and other polymer-bonded dyes. Specifically, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelate azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments In addition, quinophthalone pigments, dyed lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments and the like can be used.

  These pigments may be used without surface treatment, or may be used after surface treatment. The surface treatment method includes a method of surface coating with a resin or wax, a method of attaching a surfactant, a method of bonding a reactive substance (eg, silane coupling agent, epoxy compound, polyisocyanate, etc.) to the pigment surface, etc. Can be considered. The above-mentioned surface treatment methods are described in “Characteristics and Applications of Metal Soap” (Shobobo), “Printing Ink Technology” (CMC Publishing, 1984) and “Latest Pigment Application Technology” (CMC Publishing, 1986). Yes.

  The particle diameter of the pigment is preferably in the range of 0.01 μm to 10 μm, and preferably in the range of 0.05 μm to 1 μm, from the viewpoint of stability in the dispersion and uniformity when the layer is formed. Is more preferable, and it is particularly preferable to be in the range of 0.1 μm to 1 μm.

  As a method for dispersing the pigment, a known dispersion technique used in ink production, toner production, or the like 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 Applied Technology" (CMC Publishing, 1986).

  Hereinafter, specific examples of the sensitizing dye having a multipoint hydrogen bonding group in the present invention, in which a multipoint hydrogen bonding group is introduced into these sensitizing dyes, are shown below.

  The sensitizing dye having a multipoint hydrogen bonding group in the present invention may be used alone or in combination of two or more, and further has no multipoint hydrogen bonding group. Other sensitizing dyes may be used in combination. The other sensitizing dye is used in an amount of 1 to 90% by mass, preferably 1 to 70% by mass, and more preferably 1 to 50% by mass with respect to the total mass of the sensitizing dye component. As other sensitizing dyes, conventionally known sensitizing dyes can be used without limitation, and specifically, the sensitizing dyes listed above into which a multipoint hydrogen bonding group is introduced are preferably used.

  The sensitizing dye having a multipoint hydrogen bonding group in the present invention is 0.01 to 50% by mass, preferably 0.1%, based on the total solid content constituting the polymerizable composition, from the viewpoint of sensitivity and film strength. In the case of a dye, particularly preferably in the case of a dye, 0.5 to 10% by mass, and particularly in the case of a pigment, it can be added in a proportion of preferably 0.1 to 10% by mass.

The sensitizing dye having a multipoint hydrogen bonding group may be added directly to the polymerizable composition together with other components, but it is the same even if another layer adjacent to this is provided and added thereto. The effect of can be obtained.
In particular, when the polymerizable composition of the present invention is used in the photosensitive layer of a lithographic printing plate precursor described later, it may be added to the same layer as the image photosensitive layer, but another layer adjacent to this may be provided. Even if it is added thereto, the same effect can be obtained. Further, when the polymerizable composition of the present invention is used for the photosensitive layer of a lithographic printing plate precursor, the same content is preferable.

[(5) Additives having multipoint hydrogen bonding groups]
In the polymerizable composition of the present invention, a compound having a multipoint hydrogen bonding group may be used as an essential component, and a compound having a multipoint hydrogen bonding group may be used as an optional component additive.
Hereinafter, the additive having a multipoint hydrogen bonding group will be described.
Examples of the additive having a multipoint hydrogen bonding group in the present invention include a compound obtained by reacting a raw material represented by the general formula (II) with a polyhydric alcohol, and a raw material represented by the following general formula (IV). A compound obtained by reacting with a monoisocyanate compound is used.

In general formula (IV), R ¹ and R ² each independently represents a hydrogen atom or an organic group such as a hydrocarbyl group. R ¹ and R ² may be linked to form a cyclic structure.
R ¹ and R ² in the general formula (IV) has the same meaning as R ¹ and R ² in the general formula (I), and preferred examples are also the same.

  Hereinafter, specific examples of the additive having a multipoint hydrogen bonding group are shown.

As the additive having a multipoint hydrogen bonding group, one kind may be used alone, or two or more kinds may be mixed and used.
From the viewpoint of film strength and sensitivity, the additive having a multipoint hydrogen bonding group in the present invention is preferably in the range of 1 to 99% by mass, and 5 to 80% by mass with respect to the total solid content constituting the polymerizable composition. % Is more preferable, and the range of 10 to 60% by mass is most preferable.

In addition, the additive having a multipoint hydrogen bonding group may be added directly to the polymerizable composition together with other components. However, a similar layer may be provided by adding another layer adjacent thereto. An effect can be obtained.
In particular, when the polymerizable composition of the present invention is used in the photosensitive layer of a lithographic printing plate precursor described later, it may be added to the same layer as the image photosensitive layer, but another layer adjacent to this may be provided. Even if it is added thereto, the same effect can be obtained. Further, when the polymerizable composition of the present invention is used for the photosensitive layer of a lithographic printing plate precursor, the same content is preferable.

[Other additives]
In addition to the essential component and the additive having a multipoint hydrogen bonding group, other components suitable for its use, production method and the like can be appropriately added to the polymerizable composition of the present invention. Hereinafter, other preferable additives will be described.

[Polymerization inhibitor]
In the polymerizable composition of the present invention, for example, to prevent unnecessary thermal polymerization of a compound having a polymerizable ethylenically unsaturated double bond during production or storage of a negative photosensitive layer coating solution composition. It is desirable to add a small amount of a thermal polymerization inhibitor. Suitable thermal polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol ), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like. The addition amount of the thermal polymerization inhibitor is preferably about 0.01% by mass to about 5% by mass with respect to the mass of the nonvolatile components in the entire composition. If necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to prevent polymerization inhibition due to oxygen, and it may be unevenly distributed on the surface of the photosensitive layer in the course of drying after coating. . The addition amount of the higher fatty acid derivative is preferably about 0.5% by mass to about 10% by mass with respect to the nonvolatile components in the entire composition.

[Colorant]
A dye or a pigment may be added to the polymerizable composition of the present invention for the purpose of coloring. Thereby, when the polymerizable composition of the present invention is applied to the photosensitive layer of the lithographic printing plate precursor, so-called plate inspection properties such as visibility after plate making and image density measuring device suitability can be improved. As the colorant, many dyes cause a decrease in the sensitivity of the photopolymerization type photosensitive layer. Therefore, it is particularly preferable to use a pigment as the colorant. Specific examples include pigments such as phthalocyanine pigments, azo pigments, carbon black and titanium oxide, and dyes such as ethyl violet, crystal violet, azo dyes, anthraquinone dyes, and cyanine dyes. The addition amount of the dye and the pigment is preferably about 0.5% by mass to about 5% by mass with respect to the nonvolatile components in the whole composition.

[Other additives]
Furthermore, in order to improve the physical properties of the cured film, an inorganic filler, other plasticizers, and ink attachment on the surface of the photosensitive layer when the polymerizable composition of the present invention is applied to the photosensitive layer of a lithographic printing plate precursor are used. You may add well-known additives, such as a fat-sensitizing agent which can improve meat | flesh property. Examples of plasticizers include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin, and addition polymerization with binder polymer. Generally, it can be added in a range of 10% by mass or less based on the total mass with the compound. Further, for the purpose of improving the film strength (printing durability), which will be described later, a UV initiator, a thermal crosslinking agent, or the like can be added to enhance the effect of heating and exposure after development.

<Application to lithographic printing plate precursor>
When the polymerizable composition of the present invention is applied to the photosensitive layer of a lithographic printing plate precursor, it is prepared by dissolving the constituent components of the polymerizable composition in a suitable organic solvent and applying it to a support.
Solvents used here include acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, Acetylacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, methyl lactate, lactic acid There is ethyl. These solvents can be used alone or in combination. The solid content in the coating solution is suitably 2 to 50% by mass.

The coating amount of the photosensitive layer mainly affects the sensitivity of the photosensitive layer, the developability, and the strength and printing durability of the exposed film, and is preferably selected as appropriate according to the application. When the coating amount is too small, the printing durability is not sufficient. On the other hand, if the amount is too large, the sensitivity is lowered, it takes time for exposure, and a longer time is required for development processing, which is not preferable. For the lithographic printing plate precursor for scanning exposure which is the main object of the present invention, the coating amount is suitably in the range of about 0.1 g / m ² to about 10 g / m ² in terms of the mass after drying. More preferably from 0.5 to 5 g / m ^2.

[Support]
When the polymerizable composition of the present invention is applied to the photosensitive layer of a lithographic printing plate precursor, a conventionally used hydrophilic support used in the lithographic printing plate precursor can be used without limitation as a support used. it can.
The support used is preferably a dimensionally stable plate, for example, paper, paper laminated with plastic (eg, polyethylene, polypropylene, polystyrene, etc.), 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.), Paper or plastic film, etc. on which such metals are laminated or vapor-deposited are included. Appropriately known physical and chemical treatments are applied to these surfaces for the purpose of imparting hydrophilicity and improving strength as necessary. You may give it.

  In particular, preferred supports include paper, polyester film or aluminum plate, among which dimensional stability is good, relatively inexpensive, and a surface with excellent hydrophilicity and strength is provided by surface treatment as required. An aluminum plate that can be formed is more preferable. A composite sheet in which an aluminum sheet is bonded on a polyethylene terephthalate film as described in Japanese Patent Publication No. 48-18327 is also preferable.

An aluminum plate is a metal plate mainly composed of dimensionally stable aluminum. In addition to a pure aluminum plate, an alloy plate containing aluminum as a main component and containing a trace amount of foreign elements, or aluminum (alloy) is laminated. Or it is chosen from the vapor-deposited plastic film or paper. In the following description, the above-mentioned support made of aluminum or an aluminum alloy is generically used as an aluminum support. Examples of the foreign element contained in the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, and titanium. The content of the foreign element in the alloy is 10% by mass or less. In the present invention, a pure aluminum plate is suitable. However, since pure aluminum is difficult to manufacture in terms of refining technology, it may contain slightly different elements. Thus, the composition of the aluminum plate applied to the present invention is not specified, and it is a conventionally known material such as JIS A 1050, JIS A 1100, JIS A 3103, JIS A 3005, etc. Can be used as appropriate.
Moreover, the thickness of the aluminum support body used for this invention is about 0.1 mm-about 0.6 mm. This thickness can be appropriately changed depending on the size of the printing press, the size of the printing plate, and the user's desire. The aluminum support may be subjected to a support surface treatment described later as necessary. Of course, it may not be applied.

(Roughening treatment)
Examples of the surface roughening method include mechanical surface roughening, chemical etching, and electrolytic grain as disclosed in JP-A-56-28893. Furthermore, the electrochemical surface roughening method in which the surface is electrochemically roughened in hydrochloric acid or nitric acid electrolyte solution, the aluminum surface is scratched with a metal wire, the wire brush grain method, the surface of the aluminum is polished with a polishing ball and an abrasive. A mechanical graining method such as a pole grain method, a brush grain method in which the surface is roughened with a nylon brush and an abrasive, can be used, and the above roughening methods can be used alone or in combination. Among them, a method usefully used for roughening is an electrochemical method in which roughening is performed chemically in hydrochloric acid or nitric acid electrolyte, and a suitable amount of electricity at the time of anode is 50 C / dm ^{2 to} 400 C / dm ² . It is a range. More specifically, in the electrolytic solution containing from 0.1 to 50% hydrochloric acid or nitric acid, the temperature 20 to 80 ° C., for 1 second to 30 minutes, alternating at a current density of 100C / dm ² ~400C / dm ² It is preferable to perform direct current electrolysis.

  The roughened aluminum support may be chemically etched with acid or alkali. Etching agents suitably used are caustic soda, sodium carbonate, sodium aluminate, sodium metasilicate, sodium phosphate, potassium hydroxide, lithium hydroxide, and the like. Preferred ranges of concentration and temperature are 1 to 50% and 20%, respectively. ~ 100 ° C. Pickling is performed to remove dirt (smut) remaining on the surface after etching. As the acid used, nitric acid, sulfuric acid, phosphoric acid, chromic acid, hydrofluoric acid, borohydrofluoric acid and the like are used. In particular, as a method for removing smut after the electrochemical surface roughening treatment, contact with 15 to 65 mass% sulfuric acid at a temperature of 50 to 90 ° C. as described in JP-A-53-12739 is preferable. And the alkali etching method described in Japanese Patent Publication No. 48-28123. After the treatment as described above, the method condition is not particularly limited as long as the center line average roughness Ra of the treatment surface is preferably 0.2 to 0.5 μm.

(Anodizing treatment)
The aluminum support treated as described above is preferably anodized after that.
In the anodizing treatment, sulfuric acid, phosphoric acid, oxalic acid, or an aqueous solution of boric acid / sodium borate is used alone or in combination as a main component of the electrolytic bath. In this case, the electrolyte solution may of course contain at least components normally contained in at least an Al alloy plate, an electrode, tap water, groundwater and the like. Further, the second and third components may be added. Here, the second and third components are, for example, metal ions such as Na, K, Mg, Li, Ca, Ti, Al, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn, and ammonium ions. Examples include cations, nitrate ions, carbonate ions, chloride ions, phosphate ions, fluorine ions, sulfite ions, titanate ions, silicate ions, borate ions and the like, and the concentration is 0 to 10,000 ppm. May be included. There are no particular limitations on the conditions of the anodizing treatment, but the treatment is preferably carried out by direct current or alternating current electrolysis at a current density of 0.1 to 40 A / m ² at 30 to 500 g / liter, a treatment liquid temperature of 10 to 70 ° C. . The thickness of the formed anodic oxide film is in the range of 0.5 to 1.5 μm. Preferably it is the range of 0.5-1.0 micrometer. The support prepared by the above treatment is treated so that the pore diameter of the micropores existing in the anodized film is in the range of 5 to 10 nm and the pore density is in the range of 8 × 10 ¹⁵ to 2 × 10 ¹⁶ pieces / m ^2. It is preferred that the conditions are selected.

A widely known method can be applied as the hydrophilic treatment on the surface of the support. As a particularly preferable treatment, a hydrophilic treatment with silicate or polyvinylphosphonic acid is performed. A film | membrane is formed by 2-40 mg / m < ² > as Si or P element amount, More preferably, it is 4-30 mg / m < ² >. The coating amount can be measured by fluorescent X-ray analysis.

  The hydrophilization treatment is carried out by applying an anodized film to an aqueous solution containing 1 to 30% by mass, preferably 2 to 15% by mass of alkali metal silicate or polyvinylphosphonic acid, and having a pH of 10 to 13 at 25 ° C. This is carried out by immersing the aluminum support on which is formed, for example, at 15 to 80 ° C. for 0.5 to 120 seconds.

  As the alkali metal silicate used for the hydrophilization treatment, sodium silicate, potassium silicate, lithium silicate, or the like is used. Examples of the hydroxide used for increasing the pH of the aqueous alkali metal silicate solution include sodium hydroxide, potassium hydroxide, and lithium hydroxide. In addition, you may mix | blend alkaline-earth metal salt or a group IVB metal salt with said process liquid. Alkaline earth metal salts include nitrates such as calcium nitrate, strontium nitrate, magnesium nitrate, and barium nitrate, and water-soluble substances such as sulfate, hydrochloride, phosphate, acetate, oxalate, and borate. Salt. Group IVB metal salts include titanium tetrachloride, titanium trichloride, potassium titanium fluoride, potassium titanium oxalate, titanium sulfate, titanium tetraiodide, zirconium chloride, zirconium dioxide, zirconium oxychloride, zirconium tetrachloride, etc. Can be mentioned.

  Alkaline earth metal salts or Group IVB metal salts can be used alone or in combination of two or more. A preferable range of these metal salts is 0.01 to 10% by mass, and a more preferable range is 0.05 to 5.0% by mass. Silicate electrodeposition as described in US Pat. No. 3,658,662 is also effective. Surface obtained by combining a support with electrolytic grains as disclosed in JP-B-46-27481, JP-A-52-58602, JP-A-52-30503, and the above anodizing treatment and hydrophilization treatment Processing is also useful.

[Middle layer]
In the lithographic printing plate precursor as an application example of the present invention, an intermediate layer (also referred to as an undercoat layer) may be provided for the purpose of improving the adhesion and soiling between the photosensitive layer and the support. Specific examples of such an intermediate layer include JP-B-50-7481, JP-A-54-72104, JP-A-59-101651, JP-A-60-149491, JP-A-60-232998, JP-A-3-56177, JP-A-4-282737, JP-A-5-16558, JP-A-5-246171, JP-A-7-159983, JP-A-7-314937, JP-A-8-202025, Special Kaihei 8-320551, JP 9-34104, JP 9-236911, JP 9-269593, JP 10-69092, JP 10-115931, JP 10-161317, JP 10-260536, JP-A-10-282682, JP-A-11-84684, Japanese Patent Application No. 8-225335, Japanese Patent Application No. 8-270098, Japanese Patent Application No. 9-195863, Japanese Patent Application No. 9-195864, Japanese Patent Application No. 9-89646, Japanese Patent Application No. 9-106068, Japanese Patent Application No. 9-183834, Japanese Patent Application No. 9-264411, Japanese Patent Application No. 9 -127232, Japanese Patent Application No. 9-245419, Japanese Patent Application No. 10-127602, Japanese Patent Application No. 10-170202, Japanese Patent Application No. 11-36377, Japanese Patent Application No. 11-165661, Japanese Patent Application No. 11-284091 No., Japanese Patent Application No. 2000-14697, and the like.

[Protective layer]
Since the lithographic printing plate precursor having a photosensitive layer to which the polymerizable composition of the present invention is applied is usually exposed in the air, it is further called a protective layer (also called an overcoat layer) on the photosensitive layer. ) Is preferably provided. The protective layer prevents exposure of low molecular weight compounds such as oxygen and basic substances present in the atmosphere that hinder the image formation reaction caused by exposure in the photosensitive layer, and enables exposure in the atmosphere. To do. Therefore, the properties desired for such a protective layer are low permeability of low-molecular compounds such as oxygen, and further, transmission of light used for exposure is not substantially inhibited, and adhesion to the photosensitive layer is excellent. And it is desirable that it can be easily removed in the development process after exposure. Such a device relating to the protective layer has been conventionally devised and is described in detail in US Pat. No. 3,458,311 and Japanese Patent Publication No. 55-49729.

  As a material that can be used for the protective layer, for example, a water-soluble polymer compound having relatively excellent crystallinity is preferably used. Specifically, polyvinyl alcohol, polyvinyl pyrrolidone, acidic celluloses, gelatin, gum arabic, Water-soluble polymers such as acrylic acid are known, but among these, the use of polyvinyl alcohol as a main component gives the best results in terms of basic properties such as oxygen barrier properties and development removability. The polyvinyl alcohol used for the protective layer may be partially substituted with an ester, an ether and 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. Specific examples of polyvinyl alcohol include those having a hydrolysis rate of 71 to 100% and a molecular weight in the range of 300 to 2400. Specifically, Kuraray Co., Ltd. PVA-105, PVA-110, PVA-117, PVA-117H, PVA-120, PVA-124, PVA-124H, PVA-CS, PVA-CST, PVA-HC, PVA-203, PVA-204, PVA-205, PVA-210, PVA-217, PVA-220, PVA-224, PVA-217EE, PVA-217E, PVA-220E, PVA-224E, PVA-405, PVA- 420, PVA-613, L-8 and the like.

Components of the protective layer (selection of PVA, use of additives), coating amount, and the like are selected in consideration of fogging, adhesion, and scratch resistance in addition to oxygen barrier properties and development removability. In general, the higher the hydrolysis rate of the PVA used (the higher the content of the unsubstituted vinyl alcohol unit in the protective layer), the thicker the film thickness, the higher the oxygen barrier property, which is advantageous in terms of sensitivity. However, when the oxygen barrier property is extremely increased, there arises a problem that unnecessary polymerization reaction occurs during production and raw storage, and unnecessary fogging and image line thickening occur during image exposure. In addition, adhesion to the image area and scratch resistance are extremely important in handling the plate. That is, when a hydrophilic layer made of a water-soluble polymer is laminated on an oleophilic photosensitive layer, film peeling due to insufficient adhesive force is likely to occur, and the peeled part causes defects such as poor film hardening due to inhibition of oxygen polymerization. On the other hand, various proposals have been made to improve the adhesion between these two layers. For example, U.S. Patent Application No. 292,501 and U.S. Patent Application No. 44,563 disclose an acrylic emulsion or a water-insoluble vinylpyrrolidone-vinyl acetate copolymer in a hydrophilic polymer mainly composed of polyvinyl alcohol. It is described that sufficient adhesiveness can be obtained by mixing 20 to 60% by mass and the like and laminating on the photosensitive layer.
Any of these known techniques can be applied to the protective layer in the present invention. Such a coating method of the protective layer is described in detail in, for example, US Pat. No. 3,458,311 and JP-B-55-49729.

In order to make the lithographic printing plate precursor according to the present invention, at least exposure and development processes are performed.
As a light source for exposing the negative planographic printing plate precursor according to the present invention, a known light source can be used without limitation. The wavelength of a desirable light source is 300 nm to 1200 nm, and specifically, it is preferable to use various lasers as the light source, and among them, an infrared laser having a wavelength of 780 nm to 1200 nm is preferably used.
The exposure mechanism may be any of an internal drum system, an external drum system, a flat bed system, and the like.

  In addition, as other exposure light rays for the lithographic printing plate precursor according to the present invention, ultrahigh pressure, high pressure, medium pressure, low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, various visible and ultraviolet lasers A lamp, a fluorescent lamp, a tungsten lamp, sunlight, etc. can also be used.

  The lithographic printing plate precursor according to the invention is developed after being exposed. As the developer used in such development processing, an alkaline aqueous solution having a pH of 14 or less is particularly preferred, and an alkaline aqueous solution having a pH of 8 to 12 containing an anionic surfactant is more preferably used. For example, tribasic sodium phosphate, potassium, ammonium, dibasic sodium phosphate, potassium, ammonium, sodium carbonate, potassium, ammonium, sodium bicarbonate, potassium, ammonium, sodium borate, Examples include inorganic alkaline agents such as potassium, ammonium, sodium hydroxide, ammonium, potassium and lithium. Moreover, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, Organic alkali agents such as ethyleneimine, ethylenediamine, and pyridine are also used. These alkali agents are used alone or in combination of two or more.

In the development processing of the lithographic printing plate precursor according to the present invention, 1 to 20% by mass of an anionic surfactant is added to the developer, and more preferably 3 to 10% by mass. If the amount is too small, the developability deteriorates. If the amount is too large, the strength such as the abrasion resistance of the image deteriorates. Anionic surfactants include, for example, sodium salt of lauryl alcohol sulfate, ammonium salt of lauryl alcohol sulfate, sodium salt of octyl alcohol sulfate, such as sodium salt of isopropyl naphthalene sulfonic acid, sodium salt of isobutyl naphthalene sulfonic acid, polyoxy Higher carbon number such as sodium salt of ethylene glycol mononaphthyl ether sulfate ester, sodium salt of dodecylbenzene sulfonic acid, alkylaryl sulfonate such as sodium salt of metanitrobenzene sulfonic acid, secondary sodium alkyl sulfate, etc. Aliphatic alcohol phosphates such as alcohol sulfates, sodium salts of cetyl alcohol phosphates, eg C _{17 H 33 CON (CH 3)} CH 2 CH 2 SO 3 sulfonates of alkylamides such as Na, for example, sodium sulfosuccinate dioctyl ester, sulfonate of dibasic aliphatic esters such as sodium sulfosuccinate dihexyl ester Salts are included.

  If necessary, an organic solvent such as benzyl alcohol mixed with water may be added to the developer. As the organic solvent, those having a solubility in water of about 10% by mass or less are suitable, and preferably selected from those having 5% by mass or less. For example, 1-phenylethanol, 2-phenylethanol, 3-phenylpropanol, 1,4-phenylbutanol, 2,2-phenylbutanol, 1,2-phenoxyethanol, 2-benzyloxyethanol, o-methoxybenzyl alcohol, m -Methoxybenzyl alcohol, p-methoxybenzyl alcohol, benzyl alcohol, cyclohexanol, 2-methylcyclohexanol, 4-methylcyclohexanol, 3-methylcyclohexanol and the like can be mentioned. The content of the organic solvent is preferably 1 to 5% by mass with respect to the total mass of the developer at the time of use. The amount used is closely related to the amount of surfactant used, and it is preferable to increase the amount of anionic surfactant as the amount of organic solvent increases. This is because when the amount of the organic solvent is large and the amount of the anionic surfactant is small, the organic solvent is not dissolved, so that it is impossible to expect good developability.

Furthermore, additives such as an antifoaming agent and a hard water softening agent can be further contained as necessary. Examples of the hard water softener include Na ₂ P ₂ O ₇ , Na ₅ P ₃ O ₃ , Na ₃ P ₃ O ₉ , Na ₂ O ₄ P (NaO ₃ P) PO ₃ Na ₂ , Calgon (sodium polymetaphosphate) Such as polyphosphates, aminopolycarboxylic acids (eg, ethylenediaminetetraacetic acid, its potassium salt, its sodium salt; diethylenetriaminepentaacetic acid, its potassium salt, its sodium salt; triethylenetetraminehexaacetic acid, its potassium salt, its sodium salt Hydroxyethylethylenediaminetriacetic acid, its potassium salt, its sodium salt; nitrilotriacetic acid, its potassium salt, its sodium salt; 1,2-diaminocyclohexanetetraacetic acid, its potassium salt, its sodium salt; 1,3-diamino-2 -Propanol tetraacetic acid, its potassium salt, Sodium salt), other polycarboxylic acids (eg 2-phosphonobutanetricarboxylic acid-1,2,4, potassium salt thereof, sodium salt thereof; 2-phosphonobutanone tricarboxylic acid-2,3,4, Potassium salt, sodium salt thereof, etc., organic phosphonic acids (eg, 1-phosphonoethanetricarboxylic acid-1,2,2, potassium salt, sodium salt thereof; 1-hydroxyethane-1,1-diphosphonic acid, Potassium salt, sodium salt thereof; aminotri (methylenephosphonic acid), potassium salt thereof, sodium salt thereof and the like. The optimum amount of such a hard water softener varies depending on the hardness of the hard water used and the amount used, but is generally 0.01 to 5% by weight, more preferably in the developer at the time of use. It is made to contain in 0.01-0.5 mass%.

  Furthermore, when the lithographic printing plate precursor is developed using an automatic developing machine, the developing solution becomes fatigued according to the processing amount, so that the processing ability is restored by using a replenishing solution or a fresh developing solution. May be. In this case, it is preferable to replenish by the method described in US Pat. No. 4,882,246. Developers described in JP-A-50-26601, 58-54341, JP-B-56-39464, 56-42860, and 57-7427 are also preferable.

  The lithographic printing plate precursor thus developed is subjected to washing water, surface activity as described in JP-A Nos. 54-8002, 55-11545, 59-58431, and the like. It may be post-treated with a rinsing liquid containing an agent, a desensitizing liquid containing gum arabic, starch derivatives, and the like. These treatments can be used in various combinations for the post-treatment of the lithographic printing plate precursor according to the invention.

As the plate making process of the lithographic printing plate precursor according to the present invention, the entire surface may be heated before exposure, during exposure, and between exposure and development, if necessary. By such heating, the image forming reaction in the photosensitive layer is promoted, and advantages such as improvement in sensitivity and printing durability and stabilization of sensitivity may occur. Further, for the purpose of improving the image strength and printing durability, it is also effective to subject the developed image to full post heating or full exposure.
Usually, heating before development is preferably performed under mild conditions of 150 ° C. or less. If the temperature is too high, problems such as causing an undesired curing reaction in the non-image area are caused. Very strong conditions can be used for heating after development. Usually, the heating temperature is 200 to 500 ° C. If the heating temperature after development 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.

The planographic printing plate obtained by the above processing is loaded on an offset printing machine and used for printing a large number of sheets.
As plate cleaners used for removing stains on the plate during printing, conventionally known plate cleaners for PS plates are used. For example, CL-1, CL-2, CP, CN-4, CN, CG-1, PC-1, SR, IC (made by Fuji Photo Film Co., Ltd.), etc. are mentioned.

  EXAMPLES Hereinafter, although this invention is demonstrated using an Example, this invention is not limited to these.

[Synthesis Example 1: Synthesis of binder polymer P-6 having a multipoint hydrogen bonder]
<Synthesis of Compound SM-1>
Karenz MOI (manufactured by Showa Denko KK) (45 g) (manufactured by Wako Pure Chemical Industries, Ltd.), 6-amino-1-methyluracil (25 g) (manufactured by Tokyo Chemical Industry), dilauric acid on a 1 L eggplant flask equipped with a condenser Put 5 drops of di-n-butyltin (manufactured by Tokyo Chemical Industry) and N, N-dimethylacetamide (100 g) (manufactured by Wako Pure Chemical Industries, Ltd.), pyridine (100 g) (manufactured by Wako Pure Chemical Industries, Ltd.), 120 ° C. And stirred for 6 hours. Then, it stood to cool to room temperature, the depositing solid was filtered and vacuum-dried, and compound SM-1 (63g) of the following structure was obtained. Identification was performed by ¹ H-NMR and FT-IR spectrum.

<Synthesis of Binder Polymer P-6 with Multipoint Hydrogen Bonder>
In a 1 L three-necked flask equipped with a condenser, compound SM-1 (42.04 g) obtained by the above synthesis, compound SM-2 (69.78 g) having the following structure, light ester HO-MS (23.04 g) (Kyoeisha) Chemical Co., Ltd.), dimethyl azobisisobutyrate (0.69 g) (manufactured by Wako Pure Chemical Industries, Ltd.), and N, N-dimethylacetamide (314 g) (manufactured by Wako Pure Chemical Industries, Ltd.), and under nitrogen flow Stir at 80 ° C. for 5 hours. Thereafter, N, N-dimethylacetamide (465 g) (manufactured by Wako Pure Chemical Industries, Ltd.) and 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (free radical) (0. 52 g) and 1,8-diazabicyclo [5,4,0] -7-undecene (133.21 g) (manufactured by Tokyo Chemical Industry Co., Ltd.) were added and stirred at room temperature for 24 hours. Furthermore, methanesulfonic acid (84.11 g) (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise to the reaction solution in an ice bath, and then the reaction solution was poured into 10 L of water to precipitate a white solid, which was filtered off. After vacuum drying, a white solid (98 g) was obtained. Identification was performed by gel permeation chromatography and titration. As a result, the weight average molecular weight was 100,000 (polystyrene conversion) and the acid value was 0.87 mmol / g.

[Synthesis Example 2: Synthesis of binder polymer P-5 having a multipoint hydrogen bonder]
<Synthesis of Compound SM-3>
Compound SM-3-1 (40 g), trimethylolethane (50 g) (manufactured by Tokyo Chemical Industry) having the following structure, obtained by the method described in Advanced Materials, Vol. 12, pages 874 to 878 (2000), dilauric acid di -6 drops of n-butyltin (manufactured by Tokyo Chemical Industry) and pyridine (300 g) (manufactured by Wako Pure Chemical Industries, Ltd.) were placed in a 1 L eggplant flask and refluxed for 6 hours. Thereafter, pyridine was distilled off under reduced pressure, and then compound SM-3 having the following structure was obtained by column chromatography. Identification was performed by ¹ H-NMR and FT-IR spectrum.

<Synthesis of binder polymer P-5 having a multipoint hydrogen bonder>
In a 500 ml three-necked round bottom flask equipped with a condenser and a stirrer, siphenylmethane diisocyanate (11.51 g) (manufactured by Wako Pure Chemical Industries, Ltd.), hexamethylene diisocyanate (7.74 g) (manufactured by Wako Pure Chemical Industries, Ltd.), Polypropylene glycol having an average molecular weight of 1000 (23.00 g) (manufactured by Wako Pure Chemical Industries, Ltd.), cimethylolpropionic acid (9.25 g) (manufactured by Tokyo Chemical Industry), compound SM-3 (19.02 g) obtained by the above synthesis , N, N-dimethylacetamide (58 g) (manufactured by Wako Pure Chemical Industries, Ltd.) and 5 drops of di-n-butyltin diurarate (manufactured by Tokyo Chemical Industry), heated and stirred at 100 ° C. for 8 hours under a nitrogen stream. did. Then, after diluting with methanol (100 ml) and N, N-dimethylacetamide (200 ml), the mixture was poured into 4 L of water with stirring to precipitate a white polymer. The polymer was separated by filtration, washed with water, and vacuum dried to obtain a binder polymer P-5 (61 g). Identification was performed by gel permeation chromatography and titration. As a result, the weight average molecular weight was 60,000 (polystyrene conversion), and the acid value was 0.98 mmol / g.

[Synthesis Example 2: Synthesis of polymerizable compound M-3 having a multipoint hydrogen bonder]
<Synthesis of Compound SM-4>
1,1,1-tris (hydroxymethyl) ethane (120.2 g), 2-methoxypropene (75.0 g) was suspended in acetone (300 ml), 1 drop of concentrated sulfuric acid was added at 0 ° C., and 1 Stir for hours. It returned to room temperature and stirred for further 2 hours. After distilling off acetone, the fraction obtained at 70 ° C. under reduced pressure (1.7 mmHg) was collected to obtain compound SM-4, (1,4,4-trimethyl-3,5-dioxanyl having the following structure: ) Methane-1-ol (155.2 g) was obtained.

<Synthesis of Compound SM-5>
Compound SM-4 (96 g), hexamethylene diisocyanate (50 g) (manufactured by Wako Pure Chemical Industries, Ltd.), di-n-butyltin diurarate (5 drops) (manufactured by Tokyo Chemical Industry), and 2-butanone (350 g) (Wako Pure Chemical Industries, Ltd.) was placed in a 1 L eggplant flask with a condenser and refluxed for 24 hours while stirring. After distilling off 2-butanone, 2000 ml of water was added, the pH was adjusted to 1 to 2 with a 1 M aqueous hydrochloric acid solution, and the mixture was stirred at room temperature for 2 hours. Further, 300 g of sodium chloride was added to this aqueous solution, 2 L of ethyl acetate was added and stirred, and the ethyl acetate layer was separated. Anhydrous magnesium sulfate was added to the fractionated ethyl acetate layer, followed by filtration, and ethyl acetate was distilled off from the obtained filtrate to obtain Compound SM-5 (96 g) having the following structure. Identification was performed by ¹ H-NMR and FT-IR spectrum.

<Synthesis of polymerizable compound M-3 having a multipoint hydrogen bonding group>
Compound SM-5 (100 g), Compound SM-3-1 (144 g), acrylic acid chloride (44 g) (manufactured by Tokyo Chemical Industry), triethylamine (100 g) (manufactured by Wako Pure Chemical Industries, Ltd.), diuraric acid di- n-Butyltin (5 drops) and chloroform (1000 g) (manufactured by Wako Pure Chemical Industries, Ltd.) were placed in a 2 L eggplant flask and stirred at room temperature for 24 hours. Subsequently, chloroform was distilled off, and the resulting residue was purified by column chromatography to obtain polymerizable compound M-3 (152 g). Identification was performed by ¹ H-NMR and FT-IR.

  The binder polymer and polymerizable compound used in the following examples and comparative examples were also synthesized by the same method as described above.

(Examples 1-15, Comparative Examples 1-3)
In the following procedure, negative lithographic printing plate precursors of Examples 1 to 15 and Comparative Examples 1 to 3 shown in Table 2 were prepared, and printing performance was evaluated. The results are also shown in Table 2.

[Production of support]
Using a JIS A 1050 aluminum plate having a thickness of 0.24 mm and a width of 1030 mm, the treatment was continuously performed as follows.

(A) Roller-type nylon that rotates using an existing mechanical roughening device while supplying a slurry of a specific gravity of 1.12 (pumice) and water as a polishing slurry to the surface of an aluminum plate Mechanical roughening was performed with a brush. The average particle size of the abrasive was 40 to 45 μm, and the maximum particle size was 200 μm. The material of the nylon brush was 6.10 nylon, the hair length was 50 mm, and the hair diameter was 0.3 mm. The nylon brush was planted so as to be dense by making a hole in a stainless steel tube having a diameter of 300 mm. Three rotating brushes were used. The distance between the two support rollers (φ200 mm) at the bottom of the brush was 300 mm. The brush roller was pressed until the load of the drive motor that rotates the brush was 7 kW plus the load before the brush roller was pressed against the aluminum plate. The rotation direction of the brush was the same as the movement direction of the aluminum plate, and the rotation speed was 200 rpm.

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

(C) A desmut treatment was performed by spraying with a 1% by mass aqueous solution of nitric acid having a temperature of 30 ° C. (including 0.5% by mass of aluminum ions), and then washed with water by spraying. The nitric acid aqueous solution used for the desmut was the waste liquid from the step of electrochemical surface roughening using alternating current in nitric acid aqueous solution.

(D) An electrochemical surface roughening treatment was continuously performed using an alternating voltage of 60 Hz. The electrolytic solution at this time was a 1% by mass aqueous nitric acid solution (including 0.5% by mass aluminum ions and 0.007% by mass ammonium ions) at a temperature of 40 ° C. The AC power source was subjected to an electrochemical surface roughening treatment using a carbon electrode as a counter electrode using a trapezoidal rectangular wave alternating current with a time TP of 2 msec until the current value reached a peak from zero and a duty ratio of 1: 1. Ferrite was used for the auxiliary anode. The current density was 30 A / dm ² at the current peak value, and the amount of electricity was 255 C / cm ² in terms of the total amount of electricity when the aluminum plate was the anode. 5% of the current flowing from the power source was shunted to the auxiliary anode. Then, water washing by spraying was performed.

(E) The aluminum plate was etched by spraying at 32 ° C. with a caustic soda concentration of 26% by mass and an aluminum ion concentration of 6.5% by mass, the aluminum plate was dissolved by 0.2 g / m ² , and electricity was obtained using the previous AC. The removal of the smut component mainly composed of aluminum hydroxide generated during chemical roughening and the edge portion of the generated pit were dissolved to smooth the edge portion. Then, it was washed with water with a spray.

(F) A desmut treatment by spraying was performed with a 25% by weight aqueous solution of sulfuric acid having a temperature of 60 ° C. (containing 0.5% by weight of aluminum ions), and then washing with water by spraying.

(G) An anodizing apparatus of an existing two-stage feed electrolytic treatment method (first and second electrolysis unit length 6 m, first feed unit length 3 m, second feed unit length 3 m, first and second feed electrode lengths 2.4 m each ) Was used to perform anodization at a sulfuric acid concentration of 170 g / liter (containing 0.5 mass% of aluminum ions) at a temperature of 38 ° C. Thereafter, washing with water was performed by spraying. At this time, in the anodizing device, the current from the power source flows to the first power supply electrode provided in the first power supply unit, flows to the plate-like aluminum via the electrolytic solution, An oxide film is formed on the surface, passes through the electrolytic electrode provided in the first power feeding portion, and returns to the power source. On the other hand, the current from the power source flows to the second power feeding electrode provided in the second power feeding portion, similarly flows to the plate-like aluminum via the electrolytic solution, and an oxide film is formed on the surface of the plate-like aluminum by the second electrolysis portion. Although the amount of electricity fed from the power source to the first feeding unit and the amount of electricity fed from the power source to the second feeding unit are the same, the feeding current density on the oxide film surface in the second feeding unit is about It was 25 A / dm ² . In the 2nd electric power feeding part, it came to feed from the oxide film surface of 1.35 g / m < ² >. The final oxide film amount was 2.7 g / m ² . The aluminum support so far is referred to as [AS-1].

[Hydrophilic treatment]
The aluminum support [AS-1] was subjected to a silicate treatment in order to increase hydrophilicity as a non-image portion of the printing plate. In the treatment, a 1.5% aqueous solution of sodium silicate 3 was kept at 70 ° C. so that the contact time of the aluminum web was 15 seconds, and further washed with water. The adhesion amount of Si was 10 mg / m ² . This support is referred to as [AS-2].

[Coating intermediate layer]
The SG method liquid composition (sol solution) was prepared by the following procedure. The following composition was weighed in a beaker and stirred at 25 ° C. for 20 minutes.
・ Tetraethoxysilane 38g
・ 3-Methacryloxypropyltrimethoxysilane 13g
・ 85% phosphoric acid aqueous solution 12g
・ Ion exchange water 15g
・ Methanol 100g

This solution was transferred to a three-necked flask, a reflux condenser was attached, and the three-necked flask was immersed in an oil bath at room temperature. While stirring the contents of the three-necked flask with a magnetic stirrer, the temperature was raised to 50 ° C. over 30 minutes. While maintaining the bath temperature at 50 ° C., the mixture was further reacted for 1 hour to obtain a liquid composition (sol solution). This sol solution was diluted with methanol / ethylene glycol = 20/1 (mass ratio) to 0.5% by mass, coated on the aluminum substrate [AS-1] with a wheeler, and dried at 100 ° C. for 1 minute. . The coating amount at that time was 3.5 mg / m ² . This coating amount was obtained by obtaining the amount of Si element by fluorescent X-ray analysis and using it as the coating amount. The support thus prepared is referred to as [AS-3].

[Coating of photosensitive layer]
A photosensitive layer coating solution having the following composition is applied to the aluminum support treated as described above so that the dry coating amount is 1.0 to 1.2 g / m ^2, and dried at 100 ° C. for 1 minute. Formed.

(Photosensitive layer coating solution)
-Polymerizable compound (compound described in Table 2) 1.5 g
・ Binder polymer (resin listed in Table 2) 2.0 g
-Polymerization initiator (compound described in Table 2) 0.4 g
Sensitizing dye (compound described in Table 2) 0.2 g
Cosensitizing dye (compound described in Table 2) 0.4 g
・ Fluorine nonionic surfactant 0.03g
(Dai Nippon Ink Chemical Co., Ltd., MegaFuck F-177)
・ Thermal polymerization inhibitor 0.01g
(N-nitrosophenylhydroxylamine aluminum salt)
・ 2.0 g of colored pigment dispersion having the following composition
・ Methyl ethyl ketone 20.0g
・ Propylene glycol monomethyl ether 20.0g

-Colored pigment dispersion composition-
Pigment Blue 15: 6 15 parts by mass Allyl methacrylate / methacrylic acid copolymer 10 parts by mass (copolymerization molar ratio 80/20, weight average molecular weight 40,000)
· 15 parts by mass of cyclohexanone · 20 parts by mass of methoxypropyl acetate · 40 parts by mass of propylene glycol monomethyl ether

[Coating of protective layer]
On the obtained photosensitive layer, a 3% by mass aqueous solution of polyvinyl alcohol (saponification degree 98 mol%, polymerization degree 550) was applied so that the dry coating mass was 2 g / m ² and dried at 100 ° C. for 2 minutes. did.

[Exposure of planographic printing plate precursor]
Using the lithographic printing plate precursor obtained as described above, a solid image with a 532 nm, 100 mW FD • YAG laser (CSI Co., Ltd., plate jet 4) and an exposure power of 100 μJ / cm ² (standard exposure conditions). Exposure and dot image exposure at 1 to 99% (in 1% increments) at 4000 dpi and 175 lines / inch were performed.

[Development / plate making]
After the exposure, the developers listed in Table 2 and the finisher FP-2W manufactured by Fuji Photo Film Co., Ltd. were charged into an automatic processor FLP-813 manufactured by Fuji Photo Film Co., Ltd., respectively, and the developer temperature was 30 ° C. and the development time 18 The exposed plate was developed / engraved under the conditions of seconds to obtain a lithographic printing plate.

[Image area printing durability test]
R201 manufactured by Roland was used as a printing machine, and graph G (N) manufactured by Dainippon Ink & Chemicals, Inc. was used as ink. The printed matter in the solid image area was observed, and the printing durability of the image area was examined based on the number of images where the image started to fade. The larger the number, the better the printing durability.

[Non-image area soiling test]
The evaluation of the non-image area smearing property was performed by observing the printed material visually every 10,000 sheets until the image portion of the printed material began to fade in the image portion printing durability test. Until the end of the image area printing durability test, the non-image area of the printed material was evaluated as good if no stain was generated.

The binder polymer, polymerizable compound, polymerization initiator, sensitizing dye, infrared absorber, other additives, and the developer used, described in Table 2 below, will be described later in other examples and comparisons. The examples used in the examples (described in Tables 2 to 4) are shown below.
In addition, the binder polymers P-1 to P-10 described in Tables 2 to 4 are those shown as specific examples of the binder polymer having the multipoint hydrogen bonding group, and the polymerizable compound M-3 to M-7 is a specific example of the binder polymer having a multipoint hydrogen bonding group.
In addition, the binder polymers P-11 to P-13 and the polymerizable compounds M-1 and M-2 shown below are compounds that do not have a multipoint hydrogen bonding group.

<Binder polymer>

<Polymerizable compound>
M-1: Pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd .; NK ester A-TMMT)
M-2: Glycerin dimethacrylate hexamethylene diisocyanate urethane prepolymer (manufactured by Kyoeisha Chemical Co., Ltd .; UA101H)

<Polymerization initiator>

<Sensitizing dye>

<Other additives>

<Developer>
D-1: pH 10 aqueous solution having the following composition: monoethanolamine 0.1 part by mass triethanolamine 1.5 part by mass compound of the following (formula 1) 4.0 part by mass: compound of the following (formula 2) 2.5 parts by mass-Compound of the following (Formula 3) 0.2 parts by mass-Water 91.7 parts by mass

In the above (Formula 1), R ¹⁴ represents a hydrogen atom or a butyl group.

D-2: An aqueous solution having the following composition: 3.0 parts by mass of potassium silicate, 1.5 parts by mass of potassium hydroxide, 0.2 part by mass of the compound of the above formula 3 and 95.3 parts by mass of water

D-3: 10 g of an aqueous solution and sodium carbonate monohydrate having the following composition
・ Potassium bicarbonate 10g
・ Sodium isopropyl naphthalenesulfonate 15g
・ Sodium dibutylnaphthalenesulfonate 15g
-Sodium salt of ethylene glycol mononaphthyl ether monosulfate 10g
・ Sodium sulfite 1g
・ Ethylenediaminetetraacetic acid tetrasodium 0.1 g
・ Ion-exchanged water 938.9g

(Examples 16 to 30, Comparative Examples 4 to 6)
Table 3 was used in the same manner as in Examples 1 to 15 and Comparative Examples 1 to 3, except that the support described in Table 3 was used and the composition of the photosensitive layer coating solution was changed as shown in Table 3. Negative type lithographic printing plate precursors of Examples 16 to 30 and Comparative Examples 4 to 6 shown were produced. In Examples and Comparative Examples, the photosensitive layer was applied such that the coating amount after drying was 1.3 to 1.5 g / m ² .

  The resulting lithographic printing plate precursor was exposed and developed / made as described below, and in the same manner as in Examples 1 to 15 and Comparative Examples 1 to 3, [Image part printing durability test] [Non-image part] Stainability test] was conducted to evaluate the printing performance. The results are also shown in Table 3.

[Exposure of planographic printing plate precursor]
The obtained lithographic printing plate precursor was subjected to solid image exposure and 4000 dpi, 175 lines / inch using a 405 nm, 30 mW violet LD (internal drum type experimental machine) with an exposure power of 100 μJ / cm ² (standard exposure conditions). 1 to 99% (in 1% increments) of halftone dot image exposure.

[Development / plate making]
After the exposure, the developers listed in Table 3 and the finisher FP-2W manufactured by Fuji Photo Film Co., Ltd. were respectively charged in an automatic developing machine FLP-813 manufactured by Fuji Photo Film Co., Ltd. The exposed plate was developed / engraved under the conditions of seconds to obtain a lithographic printing plate.

(Examples 31-45, Comparative Examples 7-9)
[Coating of photosensitive layer]
A photosensitive layer coating solution having the following composition was prepared and applied to an aluminum support [AS-1] using a wire bar so that the coating amount after drying was 1.4 to 1.6 g / m ^2. A photosensitive layer was formed by drying at 115 ° C. for 45 seconds in a dry dryer.

(Photosensitive layer coating solution)
-Polymerizable compound (compound described in Table 4) 1.0 g
-Binder polymer (compound described in Table 4) 1.0 g
-Polymerization initiator (compound described in Table 4) 0.3 g
・ Infrared absorber (S-4) 0.08g
・ Fluorine nonionic surfactant 0.01g
(Dai Nippon Ink Chemical Co., Ltd., MegaFuck F-176)
・ Victoria Pure Blue Naphthalenesulfonate 0.04g
・ Methyl ethyl ketone 9.0g
・ Propylene glycol monomethyl ether 8.0g
・ Methanol 10.0g

[Coating of protective layer]
If necessary, a 3% by weight aqueous solution of polyvinyl alcohol (saponification degree 98 mol%, polymerization degree 550) is applied on the obtained photosensitive layer so that the dry application weight is 2 g / m ^2, and 100 ° C. For 2 minutes.

[Exposure of planographic printing plate precursor]
The Example lithographic printing plate precursor obtained as described above was output by a Creo Trendsetter 3244VFS equipped with a water-cooled 40 W infrared semiconductor laser (830 nm), output 9 W, outer drum rotation speed 210 rpm, plate surface energy 100 mJ / cm ² , The exposure was performed under the condition of a resolution of 2400 dpi.

[Development / plate making]
After the exposure, the developer described in Table 4 and the 1: 1 water dilute solution development of finisher Fuji Photo Film FN-6 were charged into an automatic processor Stablon 900N manufactured by Fuji Photo Film Co., Ltd. at 30 ° C. Development / plate making was performed to obtain a lithographic printing plate.

[Image area printing durability test]
A Lislon manufactured by Komori Corporation was used as a printing machine, and a graph G (N) manufactured by Dainippon Ink & Chemicals, Inc. was used as an ink. The printed matter in the solid image area was observed, and the printing durability of the image area was examined based on the number of images where the image started to fade. Larger numbers indicate better printing durability.

[Non-image area soiling test]
The evaluation of the non-image area smearing property was performed by observing the printed material visually every 10,000 sheets until the image portion of the printed material began to fade in the image portion printing durability test. Until the end of the image area printing durability test, the non-image area of the printed material was evaluated as good if no stain was generated.

As is clear from Tables 2 to 4, a polymerizable composition containing a binder polymer having a multipoint hydrogen bonding group and / or a polymerizable compound having a multipoint hydrogen bonding group (the polymerizable composition of the present invention) The lithographic printing plate precursor provided with the photosensitive layer is excellent in printing durability and is free from contamination in the non-image area. It can be seen that this is a lithographic printing plate precursor suitable for writing in. In particular, a lithographic printing plate precursor comprising a photosensitive layer composed of a polymerizable composition containing a binder polymer having a multipoint hydrogen bond group, a polymerizable compound having a multipoint hydrogen bond group, and the printing composition has a very high printing durability. It turned out to be excellent.
On the other hand, the lithographic printing plate precursor of the comparative example is exactly the same as the lithographic printing plate precursor of the example except that a polymerizable composition containing a binder polymer or a polymerizable composition having no multipoint hydrogen bonding group was used. Even those prepared were inferior in printing durability to the lithographic printing plate precursors of the examples, and were also inferior in soiling of non-image areas depending on the applied lithographic printing plate precursor.

Claims (2)

A polymerizable composition containing a binder polymer, a polymerizable compound, a polymerization initiator, and a sensitizing dye,
At least one of the components constituting this comprises a compound having a lone pair and a hydrogen atom capable of hydrogen bonding, and a compound having a substituent capable of forming two or more hydrogen bonds. Composition.   A lithographic printing plate precursor comprising a photosensitive layer containing the polymerizable composition according to claim 1 on a support.