JP2005077984A - Polymerizable composition and image recording material using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymerizable composition having excellent alkali solubility in an unexposed part and causing no decrease in the alkali solubility with time even when the composition is stored in a severe atmosphere such as high temperature and high humidity, and to provide an image recording material having a negative recording layer using the above polymerizable composition. <P>SOLUTION: The composition contains: (A) a dye having absorption at 700 to 1,300 nm wavelength; (B) a radical polymerization initiator having an alkali-soluble group; and (C) a compound having an ethylenically unsaturated bond. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a polymerizable composition and an image recording material which can be written with high sensitivity by an infrared laser using the polymerizable composition as a recording layer.

In recent years, the development of lasers has been remarkable. In particular, solid lasers and semiconductor lasers having a light emitting region from the near infrared region to the infrared region have been increasing in output and size. Therefore, these lasers are very useful as an exposure light source when making a plate directly from digital data such as a computer.
As an image recording medium using such a laser as an exposure light source, a thermopolymerizable recording layer containing a photothermal conversion substance, a thermal polymerization initiator that generates radicals, and a thermopolymerizable resin is known (for example, , See Patent Document 1).

Usually, a negative type image recording material constituting such a thermopolymerizable recording layer causes a polymerization reaction of a thermopolymerizable resin using a radical generated by light or heat as an initiator, and cures an exposed portion to form an image. The recording method for forming the part is used.
In such a negative type image recording material, an ionic material or a highly polar compound is added as a dye (photothermal conversion substance), a thermal polymerization initiator, or other constituents, and the reactivity and plate inspection properties are increased. It is possible to improve properties such as, but these highly polar compounds form undesired interactions with binders and polymerizable compounds used together when stored in a high temperature atmosphere, and are not exposed to light. The dissolution rate of the portion of the developer in the developing solution was lowered, and there was a problem that a residual film was likely to occur under normal development conditions.

For example, in order to achieve high sensitivity and high printing durability, it contains a compound having an ethylenically unsaturated double bond, a compound having absorption at a specific wavelength (550 to 850 nm), and a diaryliodonium salt. Polymerizable composition (for example, refer to Patent Document 2) or a thermosensitive composition whose chemical and physical properties are irreversibly changed by a compound having an onium salt and a carboxylate ion and a radical (for example, refer to Patent Document 3) ), A thermosensitive composition (see, for example, Patent Document 4) in which chemical and physical properties are irreversibly changed by a compound having an onium salt and a sulfonamide conjugate ion and a radical or acid. However, the polymerizable composition containing these highly polar compounds has a problem that it forms an interaction with other components under severe aging conditions, and the solubility in an aqueous alkali solution is reduced.
JP-A-8-108621 Japanese Examined Patent Publication No. 7-103171 JP 2001-343742 A JP 2002-6482 A

  The present invention has been made in consideration of the above-mentioned problems, and the object of the present invention is excellent in alkali solubility in unexposed areas, and it is possible to dissolve alkali over time even when stored in a severe atmosphere such as high temperature and high humidity. It is an object of the present invention to provide a polymerizable composition that does not cause deterioration of the property, and a negative recording layer using such a polymerizable composition, and an image recording material excellent in discrimination.

  As a result of intensive studies, the present inventors have found that the above object can be achieved by using a radical polymerization initiator having an alkali-soluble group as the polymerization initiator of the polymerizable composition, and to complete the present invention. It came.

That is, the polymerizable composition of the present invention comprises (A) a dye having absorption at a wavelength of 700 to 1300 nm, (B) a radical polymerization initiator having an alkali-soluble group, and (C) a compound having an ethylenically unsaturated bond. And containing.
In the present invention, the radical polymerization initiator (B) having an alkali-soluble group preferably has an onium salt structure, and the radical polymerization initiator (B) having an alkali-soluble group is a sulfonium salt. More preferably, (B) the radical polymerization initiator having an alkali-soluble group is most preferably a sulfonium salt comprising a sulfonium cation and a sulfonate anion.
Moreover, it is preferable that the polymeric composition of this invention has (D) binder polymer, and as such (D) binder polymer, what is represented by the following general formula (I) is more preferable.

(In General Formula (I), R ¹ represents a hydrogen atom or a methyl group, and R ² represents one or more atoms selected from the group consisting of a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom. The number of atoms excluding the substituent is 2 to 30. A represents an oxygen atom or —NR ³ —, and R ³ represents a hydrogen atom or a monovalent group having 1 to 10 carbon atoms. And n represents an integer of 1 to 5.)

  Furthermore, the polymerizable composition of the present invention preferably contains a compound represented by the following general formula (1).

(In the formula (1), A is the respective .R ¹ or R ² represents an aromatic group or a heterocyclic group independently represents a hydrogen atom or a monovalent substituent. In addition, R ¹ and R ^2, R ¹ and R ² and X, R ¹ and R ² and A, A and X may be bonded to each other to form a ring structure, where X is —O—, —S—, —SO ₂ —. , -NH -, - N (R 3) -, - CH 2 -, - CH (R 4) -, and ^{-C (R 4) (R 5} ) - represents a divalent linking group selected from, R ³ , R ⁴ and R ⁵ each independently represents a hydrogen atom or a monovalent substituent.)

  The image recording material of the present invention is characterized by having a layer containing the polymerizable composition on a support.

Although the operation of the present invention is not clear, the following is presumed. The polymerizable composition of the present invention uses (B) a radical polymerization initiator having an alkali-soluble group (hereinafter referred to as “specific initiator” as appropriate), whereby the specific initiator itself exhibits high polarity and is stable. A layer can be formed, and it exhibits high solubility in an aqueous alkali solution during development due to the function of an alkali-soluble group such as an acidic group or a salt thereof introduced into the molecule of the radical polymerization initiator. In addition, it is possible to suppress a decrease in alkali solubility when stored under severe conditions such as high temperature and high humidity.
Furthermore, in a preferred embodiment of the present invention, it is considered that (D) a polymer compound having a highly developable acid group in the molecule is used as the binder to further enhance the effect of suppressing the decrease in alkali solubility during forced aging. It is done.

  When such a polymerizable composition is used as a recording layer of a lithographic printing plate precursor, the non-image area exhibits good alkali developability and is also developed even when stored under severe conditions such as high temperature and high humidity. It is considered that the generation of the remaining film in the non-image area is suppressed without lowering the property. In general, when a highly polar compound such as an onium salt is used as a radical polymerization initiator, the initiator tends to adsorb to an aluminum substrate or the like as a support to generate a residual color in a non-image area. However, by introducing an alkali-soluble group into the radical polymerization initiator, it is believed that the alkali solubility of the initiator itself is improved and the occurrence of stains in the non-image area is suppressed, and excellent discrimination is obtained. It is.

  According to the present invention, a polymerizable composition that is excellent in alkali solubility in an unexposed area and does not cause a decrease in alkali solubility over time even when stored in a severe atmosphere such as high temperature and high humidity, and its An image recording material having a negative recording layer using such a polymerizable composition and excellent in discrimination can be obtained.

[Polymerizable composition]
The polymerizable composition of the present invention comprises (A) a dye having absorption at a wavelength of 700 to 1300 nm, (B) a radical polymerization initiator having an alkali-soluble group, and (C) a compound having an ethylenically unsaturated bond, It is characterized by containing. Hereinafter, each of these components will be described in detail.

[(B) Radical polymerization initiator having alkali-soluble group]
The (B) specific initiator used in the present invention may be an alkali-soluble group, specifically, an acid group having a dissociation property at a pKa of 12 or less, and an acid group by causing a chemical reaction by contact with an alkaline aqueous solution. Those having at least one of alkali-reactive groups.
In addition, the specific initiator having such an alkali-soluble group is preferably a compound that dissolves 10 g or more in 1 L of an alkaline aqueous solution at a temperature of 30 ° C. and a pH of 12, for example, from the viewpoint of the effect of the present invention, and dissolves 20 g or more. More preferably, it is a compound.

  As such an acid group having a dissociation property at pKa12 or lower, from the viewpoint of suppressing development damage, an acid group having dissociation property at pKa1 to 11 is preferable, and an acid group having dissociation property at pKa3 to 8 is particularly preferable. preferable. Specific examples include a carboxy group, a sulfonic acid group, a phosphonic acid group, a phenol group, a sulfinic acid group, a sulfonamide group, a β carbonyl ketone group, a β carbonyl ester group, a thiol group, and a thiocarbonyl group.

  The alkali-reactive group refers to a group that can be hydrolyzed into an acid group by contact with an aqueous alkali solution and neutralize with an alkali. For example, an ester group may be mentioned. Among them, a methyl ester group, a halogenated alkyl ester group, a benzyl ester group, a phenyl ester group, and an allyl ester group are preferable from the viewpoint of developability, and a methyl ester group is most preferable.

The (B) specific initiator used in the present invention has the alkali-soluble group and generates a radical by energy of light or heat or both, and has (C) an ethylenically unsaturated bond described later. If it is a compound which starts and accelerates | stimulates this polymerization reaction, there will be no restriction | limiting in particular.
Examples of the mother structure of the specific initiator that does not contain the alkali-soluble group include conventionally known thermal polymerization initiators, photopolymerization initiators, compounds having a bond with small bond dissociation energy, and the like. The compounds described in paragraphs [0052] to [0080] of Japanese Patent Application No. 2003-202961 previously filed by the applicant of the present application are preferably used.
Specifically, organic halogenated compounds, carbonyl compounds, organic peroxide compounds, azo polymerization initiators, azide compounds, metallocene compounds, hexaarylbiimidazole compounds, organic boric acid compounds, disulfonic acid compounds, oxime ester compounds, oniums And salt compounds (for example, iodonium salt, sulfonium salt, diazonium salt, pyridinium salt, etc.). Among them, from the viewpoint of reactivity and stability, organic halogenated compounds, iodonium salts, sulfonium salts are preferable, and sulfonium salts are preferable. Most preferred. Most preferred among the sulfonium salts are those having a triarylsulfonium salt structure in the cation moiety and having at least one electron-withdrawing group. Furthermore, the counter anion is preferably an organic anion, and more preferably a sulfonate anion from the viewpoint of reactivity and stability.

The specific initiator according to the present invention is not particularly limited as long as an alkali-soluble group is introduced into such a general radical polymerization initiator.
When an ionic one is used as the general radical polymerization initiator, the alkali-soluble group may be in the cation site, in the anion site, or in both of them. Preferable alkali-soluble groups possessed at the cation moiety include phenol groups and carboxy groups, and preferred alkali-soluble groups possessed at the anion moiety include ester groups, carboxy groups, and phenol groups. From this point of view, an ester group, particularly a methyl ester group is most preferable.
In addition, when an onium salt is used as the specific initiator according to the present invention, at least one alkali-soluble component other than an anion structure necessary for onium salt formation such as iodonium salt, sulfonium salt, diazonium salt, pyridinium salt, etc. Has a group.
Hereinafter, although the specific example of the specific initiator which concerns on this invention is shown, this invention is not limited to these.

The specific initiator which concerns on this invention can be used individually or in combination of 2 or more types.
As content of the specific initiator contained in the polymeric composition of this invention, it is preferable that it is 0.1-30 mass% in polymeric composition total solid, and is 1-20 mass%. More preferably, the content is 2 to 10% by mass.
Moreover, you may use together other radical polymerization initiators other than the said specific initiator with the polymeric composition of this invention. As other radical polymerization initiators that can be used in combination, in the description of the specific initiator, the general radical polymerization initiator mentioned as the mother core structure not containing an alkali-soluble group can be mentioned, and the content thereof Is preferably 0 to 50% by mass, more preferably 0 to 30% by mass, and most preferably 0 to 15% by mass in the total radical polymerization initiator including the specific initiator.

[(A) Dye having absorption at a wavelength of 700 to 1300 nm]
The (A) dye having absorption at a wavelength of 700 to 1300 nm (hereinafter referred to as “infrared absorber” as appropriate) used in the present invention is preferably a compound having an absorption maximum at a wavelength of 700 to 1300, and is easily available. From the viewpoint of suitability for a high-power laser, it is preferably an infrared-absorbing dye or pigment having an absorption maximum at a wavelength of 760 to 1200 nm. By adding such an infrared absorber, the polymerizable composition of the present invention has sensitivity in the infrared wavelength region.

  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, 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, oxonol dyes And dyes such as diimonium dyes, aminium dyes, and croconium dyes.

  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 U.S. Pat. No. 4,756,993 as formulas (I) and (II).
Moreover, the pigment | dye soluble in the organic solvent and alkaline aqueous solution which are described in Japanese Patent Application No. 2003-202961 which the applicant of this application submitted previously can also be mentioned.

  Particularly preferred among these dyes are cyanine dyes, phthalocyanine dyes, oxonol dyes, squarylium dyes, pyrylium salts, thiopyrylium dyes, and nickel thiolate complexes. Furthermore, the dyes represented by the following general formulas (a) to (e) are preferable because of excellent photothermal conversion efficiency, and the cyanine dye represented by the following general formula (a) is particularly preferable in the photosensitive resin composition of the present invention. When it is used, it is more preferable because it gives high polymerization activity and is excellent in stability and economy.

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 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 a carbon atom having 1 to 12 carbon atoms including a hetero atom. Indicates a hydrogen group. Here, the hetero atom represents N, S, O, a halogen atom, or Se.

In the above formula, Xa ^- has Za described later ^- is defined as in, 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 recording layer 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 charge neutralization 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 recording layer coating solution. Fluorophosphate ions and aryl sulfonate ions.

  Specific examples of the cyanine dye represented by the general formula (a) that can be suitably used in the present invention include those exemplified below, and paragraph numbers [0017] to [0019] of JP-A No. 2001-133969, Examples thereof include those described in JP-A-2002-40638, paragraph numbers [0012] to [0038], and Japanese Patent Application No. 2002-23360, paragraph numbers [0012] to [0023].

In the general formula (b), L represents a methine chain having 7 or more conjugated carbon atoms, the methine chain may have a substituent, and the substituents are bonded to each other to form a ring structure. Also good. Zb ⁺ represents a counter cation. Preferred counter cations include ammonium, iodonium, sulfonium, phosphonium, pyridinium, alkali metal cations (Ni ⁺ , K ⁺ , Li ⁺ ) and the like. R ^{9 to} R ¹⁴ and R ^{15 to} R ²⁰ are each independently a hydrogen atom or halogen atom, cyano group, alkyl group, aryl group, alkenyl group, alkynyl group, carbonyl group, thio group, sulfonyl group, sulfinyl group, oxy group Or a substituent selected from amino groups, or a combination of two or three of these, and may be bonded to each other to form a ring structure. Here, in the general formula (b), those in which L represents a methine chain having 7 conjugated carbon atoms and those in which R ^{9 to} R ¹⁴ and R ^{15 to} R ²⁰ all represent hydrogen atoms are easily available. From the viewpoint of the effect.

  Specific examples of the dye represented by formula (b) that can be suitably used in the present invention include those exemplified below.

In the general formula (c), Y ³ and Y ⁴ each represent an oxygen atom, a sulfur atom, a selenium atom, or a tellurium atom. M represents a methine chain having 5 or more conjugated carbon atoms. R ^{21 to} R ²⁴ and R ^{25 to} R ²⁸ may be the same or different, and are each a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a carbonyl group, a thiol group, Represents a group, a sulfonyl group, a sulfinyl group, an oxy group, or an amino group. Further, wherein Za ^- include a counter anion, Za in the general formula (a) ^- it is synonymous.

  In the present invention, specific examples of the dye represented by formula (c) that can be suitably used include those exemplified below.

In the general formula (d), R ²⁹ to R ³¹ each independently represent a hydrogen atom, an alkyl group, or an aryl group. R ³³ and R ³⁴ each independently represents an alkyl group, a substituted oxy group, or a halogen atom. n and m each independently represents an integer of 0 to 4. R ²⁹ and R ³⁰ , or R ³¹ and R ³² may be bonded to each other to form a ring, and R ²⁹ and / or R ³⁰ is R ³³ and R ³¹ and / or R ³² is R ³⁴ A ring may be bonded to each other, and when there are a plurality of R ³³ or R ³⁴ , R ³³ or R ³⁴ may be bonded to each other to form a ring. X ¹ and X ² are each independently a hydrogen atom, an alkyl group, or an aryl group, and at least one of X ¹ and X ² represents a hydrogen atom or an alkyl group. Q is a trimethine group or a pentamethine group which may have a substituent, and may form a ring structure together with a divalent organic group. Zc ⁻ represents a counter anion and has the same meaning as Za ⁻ in the general formula (a).

  In the present invention, specific examples of the dye represented by the general formula (d) that can be suitably used include those exemplified below.

In the general formula (e), R ^{35 to} R ⁵⁰ are each independently a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a hydroxyl group, or a carbonyl group that may have a substituent. Group, thio group, sulfonyl group, sulfinyl group, oxy group, amino group, and onium salt structure. M represents two hydrogen atoms or metal atoms, a halometal group, and an oxymetal group, and the metal atoms contained therein are IA, IIA, IIIB, IVB group atoms of the periodic table, first, second, second Three-period transition metals and lanthanoid elements can be mentioned, among which copper, magnesium, iron, zinc, cobalt, aluminum, titanium, and vanadium are preferable.

  In the present invention, specific examples of the dye represented by formula (e) that can be suitably used include those exemplified below.

  Examples of pigments used as infrared absorbers in the present invention include commercially available pigments and Color Index (CI) manual, “Latest Pigment Handbook” (edited by the Japan Pigment Technology Association, published in 1977), “Latest Pigment Applied Technology”. (CMC Publishing, published in 1986) and “Printing Ink Technology”, published by CMC Publishing, published in 1984).

  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, carbon black, and the like can be used. Among these pigments, carbon black is preferable.

  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 size of the pigment is preferably in the range of 0.01 μm to 10 μm, more preferably in the range of 0.05 μm to 1 μm, and particularly preferably in the range of 0.1 μm to 1 μm. When the particle size of the pigment is within this range, the polymerizable composition of the present invention is stable when the polymerizable composition is applied to the recording layer of the lithographic printing plate precursor in the image recording layer coating solution. And excellent uniformity of the image recording layer.

  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).

(A) Infrared absorber in this invention may use only 1 type, and can also use 2 or more types together.
Moreover, as such an infrared absorber, a cyanine dye is preferable.
From the viewpoint of sensitivity, the cyanine dye represented by the general formula (a) is more preferable, and among the cyanine dyes represented by the general formula (a), a cyanine dye where X ¹ is —NPh ₂ or X ² -L ¹ is used. Preferably, a cyanine dye having -NPh ₂ is more preferable. In addition, from the viewpoint of developability, the dyes described in Japanese Patent Application No. 2003-202961 are also preferred.
Further, cyanine dyes having an electron-withdrawing group or a heavy atom-containing substituent at both indolenine sites are also preferable. For example, those described in the specification of Japanese Patent Application No. 2001-6323 are preferably used. Most preferably, X ¹ is —NPh ₂ , and a cyanine dye having an electron-withdrawing group at both indolenine sites.

  When these pigments or dyes are used in combination, 0.01 to 50% by mass, preferably 0.1 to 15% by mass, particularly 0.5 to 15% by mass in the case of a dye, based on the total solid content of the polymerizable composition. In the case of a pigment, it can be added in a proportion of 0.1 to 15% by mass, preferably 1 to 10% by mass. Within this range, the polymerizable composition of the present invention has excellent composition uniformity, cures with high sensitivity, and achieves excellent film properties.

[(C) Compound having an ethylenically unsaturated bond]
The compound (C) having an ethylenically unsaturated bond (hereinafter referred to as “polymerizable compound” as appropriate) used in the present invention is an addition polymerizable compound having at least one ethylenically unsaturated double bond. And is preferably selected from compounds having at least one terminal ethylenically unsaturated bond, 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 include, for example, those having 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 of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. In addition, unsaturated carboxylic acid ester having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group, amide and monofunctional or polyfunctional isocyanate, addition reaction product of epoxy, monofunctional or A dehydration condensation reaction product with a polyfunctional carboxylic acid is also preferably used.

  In addition, an unsaturated carboxylic acid ester having an electrophilic substituent such as an isocyanate group or an epoxy group, an addition reaction product of an amide with a monofunctional or polyfunctional alcohol, amine or thiol, halogen A substitution reaction product of an unsaturated carboxylic acid ester or amide with a monofunctional or polyfunctional alcohol, amine or thiol having a leaving group such as a group or a tosyloxy group 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 2,2-bis [4- (acryloxydiethoxy) phenyl] propane, polypropylene glycol diacrylate, and the like.

  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, and JP-A-59-5240. And those having an aromatic skeleton described in JP-A-59-5241, JP-A-2-226149, and those containing an amino group described in JP-A-1-165613. 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 containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (g) to a polyisocyanate compound having two or more isocyanate groups. Compounds and the like.

In the general formula (g), R and R ′ each independently represents a hydrogen atom or CH ₃ .
Further, urethane acrylates as described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-B-58-49860, JP-B-56-17654 And urethane compounds having an ethylene oxide skeleton described in JP-B-62-39417 and JP-B-62-39418.

  Furthermore, 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 are used. Depending on the case, a polymerizable composition having an excellent curing reaction rate can be obtained.

  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. 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, 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.

  Details of how to use these compounds (C) having an ethylenically unsaturated bond, such as what structure to use, whether to use alone or in combination, and how much is added, are the final photosensitive materials It can be set arbitrarily according to the performance design. 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 further, different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrenic 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 a high hydrophobicity is not preferable in terms of development speed and precipitation in a developing solution, although it is excellent in photosensitive speed and film strength.

(C) Regarding the compounding ratio of the compound having an ethylenically unsaturated bond, a larger amount is advantageous in terms of sensitivity, but if it is too much, an undesirable phase separation occurs or a production process due to the adhesiveness of the composition The above problems (for example, defective production due to transfer of photosensitive material components and adhesion) and problems such as precipitation from a developer may occur when a lithographic printing plate precursor is used. From these viewpoints, the component (C) in the polymerizable composition of the present invention is similarly 20 to 70 mass with respect to the total solid content of the polymerizable composition when it is used for the recording layer of the lithographic printing plate precursor. % Is preferable, and 25 to 50% by mass is more preferable.
Moreover, (C) the compound which has an ethylenically unsaturated bond may be used individually by 1 type, and may be used together 2 or more types.

  In addition, when used for a lithographic printing plate precursor, (C) ethylenically unsaturated bond also has compatibility and dispersibility with other components in the recording layer (for example, binder polymer, initiator, colorant, etc.). The selection and use method of a compound having a low molecular weight is an important factor. For example, the compatibility may be improved by using a low-purity compound or using two or more kinds in combination.

[(D) Binder polymer]
The polymerizable composition of the present invention preferably contains (D) a binder polymer. (D) It is preferable to use a linear organic polymer as the binder polymer. Any such “linear organic polymer” may be used. Preferably, a linear organic high molecular weight polymer that is water-soluble or weakly alkaline water-developable and that is soluble or swellable in weakly alkaline water is selected. The linear organic high molecular polymer is selected and used not only as a film-forming agent for the composition but also according to its use as water, weak alkaline water or an organic solvent developer. For example, when a water-soluble organic polymer is used, water development is possible. Examples of such a linear organic polymer include addition polymers having a carboxylic acid group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-A-54-25957, JP-A-54-92723, JP-A-59-53836, JP-A-59-71048, and the special features previously proposed by the applicant of the present application. Those described in Japanese Patent Application No. 2002-287920, that is, a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, and a partially esterified malein Examples include acid copolymers, 2-methacryloyloxyethyl succinic acid copolymers, and 2-methacryloyloxyethyl hexahydrophthalic acid copolymers. Similarly, there is an acidic cellulose derivative having a carboxylic acid group in the side chain. In addition, those obtained by adding a cyclic acid anhydride to an addition polymer having a hydroxyl group are useful.

  Among them, from the viewpoint of suppressing damage by the developer, Japanese Patent Application No. 2002-287920 (D) binder polymer such as 2-methacryloyloxyethyl succinic acid copolymer, 2-methacryloyloxyethyl hexahydrophthalic acid copolymer, etc. It is preferable to contain the polymer which has the structural unit represented by the following general formula (I) described in the specification.

(In General Formula (I), R ¹ represents a hydrogen atom or a methyl group, and R ² represents one or more atoms selected from the group consisting of a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom. And represents a linking group having 2 to 30 atoms excluding a substituent, A represents an oxygen atom or —NR ³ —, and R ³ represents a hydrogen atom or 1 to 10 carbon atoms. Represents a monovalent hydrocarbon group, and n represents an integer of 1 to 5.)
In the above general formula (I), it is more preferable that the linking group represented by R ² has an alkylene structure or a structure in which the alkylene structure is linked via an ester bond.

Hereinafter, the structural unit represented by the general formula (I) will be described in detail.
R ¹ in the general formula (I) represents a hydrogen atom or a methyl group, and a methyl group is particularly preferable.
The linking group represented by R ² in the general formula (I) represents a linking group composed of one or more atoms selected from the group consisting of a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom and a halogen atom. And the number of atoms excluding the substituent is 2-30. Specific examples include alkylene, substituted alkylene, arylene, substituted arylene, and the like, and a structure in which a plurality of these divalent groups are linked by an amide bond or an ester bond may be used.
Examples of the linking group having a chain structure include ethylene and propylene. A structure in which these alkylenes are linked via an ester bond can also be exemplified as a preferable example.

Among these, the linking group represented by R ² in the general formula (I) is preferably an (n + 1) -valent hydrocarbon group having an aliphatic cyclic structure having 3 to 30 carbon atoms. More specifically, a compound having an aliphatic cyclic structure such as cyclopropane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, dicyclohexyl, tercyclohexyl, norbornane and the like, which may be substituted by one or more arbitrary substituents And (n + 1) valent hydrocarbon groups by removing (n + 1) hydrogen atoms on an arbitrary carbon atom constituting. R ² preferably has 3 to 30 carbon atoms including a substituent.

One or more arbitrary carbon atoms of the compound constituting the aliphatic cyclic structure may be replaced with a heteroatom selected from a nitrogen atom, an oxygen atom, or a sulfur atom. In terms of printing durability, R ² represents a condensed polycyclic aliphatic hydrocarbon, a bridged cyclic aliphatic hydrocarbon, a spiro aliphatic hydrocarbon, an aliphatic hydrocarbon ring assembly (a plurality of rings are connected by a bond or a linking group). A (n + 1) valent hydrocarbon group having an aliphatic cyclic structure which may have a substituent of 5 to 30 carbon atoms containing two or more rings. . Also in this case, the carbon number includes the carbon atom of the substituent.

As the linking group represented by R ² , those having 5 to 10 atoms are further preferable, and structurally a chain structure having an ester bond in the structure, Those having a cyclic structure are preferred.

Examples of the substituent that can be introduced into the linking group represented by R ² include monovalent nonmetallic atomic groups other than hydrogen, such as halogen atoms (—F, —Br, —Cl, —I), hydroxyl groups. Group, alkoxy group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N- Diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy , Arylsulfoxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkylureido group, N′-aryl Ureido group, N ′, N′-diarylureido group, N′-alkyl-N′-arylureido group, N-alkylureido group, N-arylureido group, N′-alkyl-N-alkylureido group, N ′ -Alkyl-N-arylureido group, N ', N'-dialkyl-N-alkylureido group, N', N'-dialkyl-N-arylureido group, N'-aryl-N-alkylureido group, N ' -Aryl-N-arylureido group, N ', N'-diaryl-N-alkylureido group, N', N'-diaryl-N-arylureido group, N'-al Kill-N′-aryl-N-alkylureido group, N′-alkyl-N′-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group and its conjugate base group, Alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, Alkylsulfinyl group An arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfo group (-SO ₃ H) and its conjugated base group, alkoxy sulfonyl group, aryloxy sulfonyl group, sulfinamoyl group, N- alkylsulfinamoyl group, N, N- Dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N -Dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, N-acylsulfamoyl group and its conjugate base group, N- alkylsulfonylsulfamoyl group (-SO ₂ NHSO ₂ alkyl)) and its conjugated base group, N- aryl sulfonylsulfamoyl group _{(-SO 2 NHSO 2 (aryl)} ) and its conjugated base group, N- alkylsulfonylcarbamoyl group (-CONHSO ₂ (alkyl)) and its conjugate Base group, N-arylsulfonylcarbamoyl group (—CONHSO ₂ (aryl)) and its conjugate base group, alkoxysilyl group (—Si (Oalkyl) ₃ ), aryloxysilyl group (—Si (Oaryl) ₃ ), hydroxysilyl Group (—Si (OH) ₃ ) and its conjugate base group, phosphono group (—PO ₃ H ₂ ) and its conjugate base group, dialkylphosphono group (—PO ₃ (alkyl) ₂ ), diarylphosphono group (— PO ₃ (aryl) _2), alkyl aryl phosphono group _{(-PO 3 (alkyl) (aryl} )) , Monoalkylphosphono group (—PO ₃ H (alkyl)) and its conjugate base group, monoarylphosphono group (—PO ₃ H (aryl)) and its conjugate base group, phosphonooxy group (—OPO ₃ H ₂ ) And its conjugate base group, dialkylphosphonooxy group (—OPO ₃ (alkyl) ₂ ), diarylphosphonooxy group (—OPO ₃ (aryl) ₂ ), alkylarylphosphonooxy group (—OPO ₃ (alkyl) ( aryl)), monoalkylphosphonooxy group (—OPO ₃ H (alkyl)) and its conjugate base group, monoarylphosphonooxy group (—OPO ₃ H (aryl)) and its conjugate base group, cyano group, nitro group, group, ₍₂ -B (alkyl)) dialkyl boryl group, Jiariruboriru group (-B (aryl) _2), alkyl aryl boryl -B (alkyl) (aryl)) , dihydroxy boryl group (-B (OH) ₂₎ and its conjugated base group, an alkyl hydroxy boryl group (-B (alkyl) (OH) ) and its conjugated base group, an aryl hydroxy boryl And the group (—B (aryl) (OH)) and its conjugate base group, aryl group, alkenyl group and alkynyl group.

  For example, when the polymerizable composition of the present invention is used as a recording layer of a lithographic printing plate precursor, depending on the design of the recording layer, a substituent having a hydrogen atom capable of hydrogen bonding, particularly an acid rather than a carboxylic acid. Substituents having an acidity with a small dissociation constant (pKa) are not preferred because they tend to lower the printing durability. On the other hand, hydrophobic substituents such as halogen atoms, hydrocarbon groups (alkyl groups, aryl groups, alkenyl groups, alkynyl groups), alkoxy groups, aryloxy groups and the like are more preferable because they tend to improve printing durability. When the cyclic structure is a monocyclic aliphatic hydrocarbon having 6 or less members such as cyclopentane or cyclohexane, it preferably has such a hydrophobic substituent. If possible, these substituents may be bonded to each other or with a substituted hydrocarbon group to form a ring, and the substituent may be further substituted.

R ³ in the case where A in the general formula (I) is —NR ³ — represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. Examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms represented by R ³ include an alkyl group, an aryl group, an alkenyl group, and an alkynyl group.
Specific examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, isopropyl group, isobutyl group, sec-butyl group, 1 carbon number such as tert-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group, cyclohexyl group, 1-adamantyl group, 2-norbornyl group Up to 10 linear, branched or cyclic alkyl groups.
Specific examples of the aryl group include carbon having one heteroatom selected from the group consisting of an aryl group having 1 to 10 carbon atoms such as a phenyl group, a naphthyl group, and an indenyl group, a nitrogen atom, an oxygen atom, and a sulfur atom. Examples include heteroaryl groups of 1 to 10, such as furyl, thienyl, pyrrolyl, pyridyl, and quinolyl groups.
Specific examples of the alkenyl group include those having 1 to 10 carbon atoms such as vinyl group, 1-propenyl group, 1-butenyl group, 1-methyl-1-propenyl group, 1-cyclopentenyl group, 1-cyclohexenyl group and the like. A linear, branched, or cyclic alkenyl group is mentioned.
Specific examples of the alkynyl group include alkynyl groups having 1 to 10 carbon atoms such as ethynyl group, 1-propynyl group, 1-butynyl group, and 1-octynyl group. The substituent that R ³ may have is the same as those exemplified as the substituent that R ² can introduce. However, the carbon number of R < ³ > is 1-10 including the carbon number of a substituent.
A in the general formula (I) is preferably an oxygen atom or —NH— because synthesis is easy.

  N in the general formula (I) represents an integer of 1 to 5, and is preferably 1 in terms of printing durability.

  Although the preferable specific example of the structural unit represented by general formula (I) which comprises the binder polymer especially suitable for this invention below is shown, it is not limited to these.

  The structural unit represented by the general formula (I) may have only one type in the binder polymer, or may have two or more different types. That is, the preferred binder polymer in the present invention may be a polymer composed only of the structural unit represented by the general formula (I), but is generally used as a copolymer combined with other copolymerization components. Is. The total content of the structural unit represented by the general formula (I) in the copolymer is appropriately determined depending on the structure, the design of the polymerizable composition, and the like, but preferably 1 to 99 with respect to the total molar amount of the polymer component. It is contained in the range of mol%, more preferably 5 to 40 mol%, still more preferably 5 to 20 mol%.

  As a copolymerization component in the case of using as a copolymer, a conventionally well-known thing can be used without a restriction | limiting, if it is a monomer which can be radically polymerized. Specific examples include monomers described in “Polymer Data Handbook—Basic Edition” (Edition of Polymer Society, Bafukan, 1986). One type of such copolymerization component may be used, or two or more types may be used in combination.

Among the above binder polymers, in particular, [allyl (meth) acrylate / (meth) acrylic acid / other addition polymerizable vinyl monomer as required] copolymer, JP-A Nos. 2000-131837 and 2002-62648. A polymer containing an acrylic group, a methacryl group or an allyl group as described in JP 2000-187322 A or Japanese Patent Application No. 2002-287920 has a balance of film strength, sensitivity, and developability. It is excellent and suitable.
In particular, a polymer having a structural unit represented by the general formula (I) and a radical polymerizable group (carbon-carbon double bond) having a structure represented by the following general formulas (II) to (IV) Is most preferred.

In general formulas (II) to (IV), R ^{4 to} R ¹⁴ each independently represents a hydrogen atom or a monovalent substituent. X and Y each independently represent an oxygen atom, a sulfur atom, or N—R ¹⁵ , and Z represents an oxygen atom, a sulfur atom, —N—R ^15, or a phenylene group. Here, R ¹⁵ represents a hydrogen atom or a monovalent organic group.

In the general formula (II), R ^{4 to} R ⁶ each independently represent a hydrogen atom or a monovalent substituent, and R ⁴ represents a hydrogen atom or an alkyl which may have a substituent. An organic group such as a group can be mentioned, and specifically, a hydrogen atom, a methyl group, a methylalkoxy group, and a methyl ester group are preferable. R ⁵ and R ⁶ may each independently have a hydrogen atom, a halogen atom, an amino group, a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, or a substituent. Alkyl group, aryl group which may have a substituent, alkoxy group which may have a substituent, aryloxy group which may have a substituent, alkylamino group which may have a substituent, substituted An arylamino group that may have a group, an alkylsulfonyl group that may have a substituent, an arylsulfonyl group that may have a substituent, and the like, among them, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group An alkyl group which may have a substituent and an aryl group which may have a substituent are preferable.
Here, examples of the substituent that can be introduced into these groups include a methoxycarbonyl group, an ethoxycarbonyl group, an isopropyloxycarbonyl group, a methyl group, an ethyl group, and a phenyl group.
X represents an oxygen atom, a sulfur atom, or —N—R ¹⁵ , where R ¹⁵ includes an alkyl group which may have a substituent.

In the general formula (III), R ^{7 to} R ¹¹ each independently represents a hydrogen atom or a monovalent substituent, and R ^{7 to} R ¹¹ are, for example, a hydrogen atom, a halogen atom, an amino group, Dialkylamino group, carboxyl group, alkoxycarbonyl group, sulfo group, nitro group, cyano group, optionally substituted alkyl group, optionally substituted aryl group, optionally substituted An alkoxy group, an optionally substituted aryloxy group, an optionally substituted alkylamino group, an optionally substituted arylamino group, an optionally substituted alkylsulfonyl group And an arylsulfonyl group which may have a substituent, among others, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl which may have a substituent It is preferred.
Here, examples of the substituent that can be introduced into these groups include those listed as substituents that can be introduced in the general formula (II).
Y represents an oxygen atom, a sulfur atom, or —N—R ¹⁵ . Examples of R ¹⁵ include the same as those in general formula (II).

In the general formula (IV), R ^{12 to} R ¹⁴ each independently represents a hydrogen atom or a monovalent substituent. Specific examples thereof include a hydrogen atom, a halogen atom, an amino group, and a dialkylamino group. A carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, Aryloxy group which may have a substituent, alkylamino group which may have a substituent, arylamino group which may have a substituent, alkylsulfonyl group which may have a substituent, substituent An arylsulfonyl group that may have a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group that may have a substituent, and an aryl group that may have a substituent. Masui.
Here, as the substituent that can be introduced into these groups, examples of the substituent that can be introduced into these groups include those listed as the substituents that can be introduced in the general formula (II).
Z represents an oxygen atom, a sulfur atom, —N—R ¹⁵ or a phenylene group. Examples of R ¹⁵ include the same as those in general formula (II).

  Among these radical polymerizable groups, a radical polymerizable group having a structure represented by the general formulas (II) and (III) is preferable.

Other binder polymers include JP-B Nos. 7-12004, 7-120041, 7-120042, 8-12424, JP-A 63-287944, and JP-A 63-287947. No. 1, Japanese Patent Application Laid-Open No. 1-271741, Japanese Patent Application No. 10-116232, etc., the urethane-based binder polymer containing an acid group is very excellent in strength. It is advantageous in terms of aptitude.
Further, the binder polymer having an amide group described in JP-A-11-171907 has excellent developability and film strength, and this binder polymer can also be applied to the present invention.

In addition, polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble linear organic polymer. In addition, in order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.
These linear organic high molecular polymers can be mixed in an arbitrary amount in the total polymerizable composition. However, when the blending amount exceeds 90% by mass, a preferable result is not given in terms of the image strength to be formed. Preferably it is 30-85 mass%. Moreover, it is preferable that the above-mentioned (C) polymerizable compound and the linear organic polymer are in the range of 1/9 to 7/3 by mass ratio.

  Each of these binder polymers may be used alone or in combination of two or more.

  The molecular weight of the (D) binder polymer in the present invention is appropriately determined from the viewpoints of image formability and printing durability, but usually the preferred molecular weight is 2,000 to 1,000,000, more preferably 5, The range is from 000 to 500,000, more preferably from 10,000 to 200,000.

  As the binder polymer (D) in the present invention, a binder polymer that is substantially insoluble in water and soluble in an alkaline aqueous solution is used. For this reason, the organic solvent which is not environmentally preferable is not used as a developing solution, or it can restrict | limit to the very small usage-amount. The acid value of the (D) binder polymer (the acid content per gram of the polymer expressed as a chemical equivalent number) and the molecular weight are appropriately selected from the viewpoint of image strength and developability. The preferred acid value is 0.4 to 3.0 meq / g, the preferred molecular weight is in the range of 2000 to 500,000, more preferably the acid value is 0.6 to 2.0, and the molecular weight is 10,000 to 300,000. Range.

[(E) Compound represented by general formula (1)]
It is preferable to add a compound represented by the following general formula (1) (hereinafter, appropriately referred to as “monocarboxylic acid compound”) to the polymerizable composition of the present invention. By adding such a compound to the polymerizable compound, the decomposition rate of the radical polymerization initiator can be improved, and further, the generated polymerization initiation radical or polymerization growth radical can undergo radical chain transfer to the monocarboxylic acid compound. It is considered that the polymerization reaction of the polymerizable compound is accelerated. Further, by adding such a compound, there is an effect that the storage stability of the radical polymerization type light-sensitive material, which was originally insufficient, is improved.

In general formula (1), A represents an aromatic group or a heterocyclic group. R ¹ and R ² each independently represents a hydrogen atom or a monovalent substituent. R ¹ and R ² , R ¹ and R ² and X, R ¹ and R ² and A, A and X may be bonded to each other to form a ring structure. X is —O—, —S—, —SO ₂ —, —NH—, —N (R ³ ) —, —CH ₂ —, —CH (R ⁴ ) — and —C (R ⁴ ) (R ⁵ )-Represents a divalent linking group selected from R, R ³ , R ⁴ or R ⁵ each independently represents a hydrogen atom or a monovalent substituent.

Here, in the general formula (1), the aromatic group represented by A includes a benzene ring, two to three benzene rings forming a condensed ring, and a benzene ring and a 5-membered unsaturated ring condensed. Examples include those that form a ring. Specific examples include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group. Among these, a phenyl group and a naphthyl group are more preferable.
In addition, the aromatic group may have a substituent, and as the aromatic group having such a substituent, a monovalent other than a hydrogen atom is used as a substituent on a ring-forming carbon atom of an aryl group described later. And those having a group consisting of a nonmetallic atomic group. In addition, as an example of the preferable substituent introduce | transduced here, what was shown as a substituent in the below-mentioned alkyl group, a substituted alkyl group, and a substituted alkyl group can be mentioned.

As the heterocyclic group represented by A, a pyrrole ring group, a furan ring group, a thiophene ring group, a benzopyrrole ring group, a benzofuran ring group, a benzothiophene ring group, a pyrazole ring group, an isoxazole ring group, an isothiazole ring group, Indazole ring group, benzisoxazole ring group, benzoisothiazole ring group, imidazole ring group, oxazole ring group, thiazole ring group, benzimidazole ring group, benzoxazole ring group, benzothiazole ring group, pyridine ring group, quinoline ring Group, isoquinoline ring group, pyridazine ring group, pyrimidine ring group, pyrazine ring group, phthalazine ring group, quinazoline ring group, quinoxaline ring group, acylidene ring group, phenanthridine ring group, carbazole ring group, purine ring group, pyran ring Group, piperidine ring group, piperazine ring group, morpholine ring group, indole ring group, Ndorijin ring group, a chromene ring group, a cinnoline ring group, an acridine ring group, a phenothiazine ring group, a tetrazole ring group, a triazine ring group, and the like.
Further, the heterocyclic group may have a substituent, and as such a substituent, a monovalent non-metallic atomic group excluding a hydrogen atom as a substituent on a ring-forming carbon atom of an aryl group described later. Those having a group consisting of: Examples of preferred substituents include the alkyl groups, substituted alkyl groups described below, and those shown as substituents in the substituted alkyl group.

Next, as the monovalent substituent represented by R ¹ and R ² in the general formula (1), a halogen atom, an amino group which may have a substituent, an alkoxycarbonyl group, a hydroxyl group, an ether group, Examples include a thiol group, a thioether group, a silyl group, a nitro group, and a cyano group, and an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and a heterocyclic group, each of which may have a substituent.

  Examples of such an alkyl group include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group. Group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group, octadecyl group, eicosyl group, isopropyl group, isobutyl group, s-butyl group, t Examples include -butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group, and 2-norbornyl group. Of these, linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, and cyclic alkyl groups having 5 to 10 carbon atoms are more preferable.

  As the substituent that such an alkyl group may have, a group consisting of a monovalent non-metallic atomic group excluding a hydrogen atom is used, and preferable examples include halogen atoms (—F, —Br, —Cl, -I), hydroxyl group, alkoxy group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-aryl Amino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarba Iroxy group, alkylsulfoxy group, arylsulfoxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkyl Ureido group, N′-arylureido group, N ′, N′-diarylureido group, N′-alkyl-N′-arylureido group, N-alkylureido group, N-arylureido group, N′-alkyl-N -Alkylureido group, N'-alkyl-N-arylureido group, N ', N'-dialkyl-N-alkylureido group, N', N'-dialkyl-N-arylureido group, N'-aryl-N -Alkylureido group, N'-aryl-N-arylureido group, N ', N'-diaryl-N-alkylureido Group, N ′, N′-diaryl-N-arylureido group, N′-alkyl-N′-aryl-N-alkylureido group, N′-alkyl-N′-aryl-N-arylureido group, alkoxycarbonyl Amino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-ary Roxycarbonylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N- Diarylcarbamoyl group, N-alkyl-N -Arylcarbamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group,

Arylsulfonyl group, sulfo group (—SO ₃ H) and its conjugate base group (referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkyls Rufiinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N- dialkylsulfamoyl group, N- aryl sulfamoyl group, N, N- diaryl sulfamoyl group, N- alkyl -N- arylsulfamoyl group, a phosphono group (-PO ₃ H ₂₎ and its conjugated base group (referred to as phosphonato group), dialkylphosphono group (-PO ₃ (alkyl) ₂₎ wherein "alk l = alkyl group, hereinafter the "diarylphosphono group (-PO3 (aryl) _2)" aryl = aryl group, hereinafter the "alkylaryl phosphono group _{(-PO 3 (alkyl) (aryl} )), monoalkyl Phosphono group (—PO ₃ (alkyl)) and its conjugate base group (referred to as alkylphosphonate group), monoarylphosphono group (—PO ₃ H (aryl)) and its conjugate base group (arylphosphonate group and ), Phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group (referred to as phosphonatoxy group), dialkylphosphonooxy group (—OPO ₃ H (alkyl) ₂ ), diarylphosphonooxy group (—OPO ₃ ( aryl) _2), alkylaryl phosphono group _{(-OPO 3 (alkyl) (aryl} )), monoalkyl phosphonates Oxy group (-OPO ₃ H (alkyl)) and its conjugated base group (alkyl referred to as phosphonic Hona preparative group), monoarylphosphono group (-OPO ₃ H (aryl)) and its conjugated base group (aryl phosphite Hona DOO Oxy group), cyano group, nitro group, aryl group, alkenyl group, alkynyl group, heterocyclic group, silyl group and the like.

  Specific examples of the alkyl group in these substituents include the above-described alkyl groups, and specific examples of the aryl group in the substituent include phenyl group, biphenyl group, naphthyl group, tolyl group, xylyl group, mesityl group, Cumenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, Methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl , It can be exemplified cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl group, a phosphate Hona preparative phenyl group.

Examples of alkenyl groups include vinyl, 1-propenyl, 1-butenyl, cinnamyl, 2-chloro-1-ethenyl, etc. Examples of alkynyl include ethynyl, 1 -Propynyl group, 1-butynyl group, trimethylsilylethynyl group and the like.
The R ⁰¹ of the acyl group (R ⁰¹ CO-), include hydrogen atom, and the above-described alkyl group, an aryl group. Among these substituents, more preferred are a halogen atom (—F, —Br, —Cl, —I), an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an N-alkylamino group, N, N. -Dialkylamino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group Group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonate group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfa group Moyl group, N-arylsulfur Amoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group, phosphonato group, dialkylphosphono group, diarylphosphono group, monoalkylphosphono group, alkylphosphonato group, monoarylphosphono group, arylphospho Examples thereof include a nato group, a phosphonooxy group, a phosphonatoxy group, an aryl group, and an alkenyl group.
Examples of the heterocyclic group include a pyridyl group and a piperidinyl group. Examples of the silyl group include a trimethylsilyl group.

  On the other hand, examples of the alkylene group in the substituted alkyl group include divalent organic residues obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. Can include linear alkylene groups having 1 to 12 carbon atoms, branched chains having 3 to 12 carbon atoms, and cyclic alkylene groups having 5 to 10 carbon atoms. Preferable specific examples of the substituted alkyl group obtained by combining such a substituent and an alkylene group include a chloromethyl group, a bromomethyl group, a 2-chloroethyl group, a trifluoromethyl group, a methoxymethyl group, and an isopropoxymethyl group. , Butoxymethyl group, s-butoxybutyl group, methoxyethoxyethyl group, allyloxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, pyridylmethyl group, tetramethylpiperidinylmethyl group, N-acetyltetra Methylpiperidinylmethyl group, trimethylsilylmethyl group, methoxyethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl Group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxycarbonylethyl group, allyloxycarbonylbutyl group, chloro Phenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) carbamoylmethyl group, Sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N-methyl-N- (phosphonov Nyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group, tolylphosphonohexyl group, tolylphosphonatohexyl Group, phosphonooxypropyl group, phosphonatoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p-methylbenzyl group, cinnamyl group, allyl group, 1- Examples thereof include a propenylmethyl group, a 2-butenyl group, a 2-methylallyl group, a 2-methylpropenylmethyl group, a 2-propynyl group, a 2-butynyl group, and a 3-butynyl group.

Examples of the aryl group include a benzene ring, a ring in which 2 to 3 benzene rings form a condensed ring, and a group in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. Specific examples include: Examples thereof include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group. Among these, a phenyl group and a naphthyl group are more preferable.
As the substituted aryl group, those having a group consisting of a monovalent nonmetallic atomic group other than a hydrogen atom as a substituent on the ring-forming carbon atom of the above-described aryl group are used. Examples of preferred substituents include the aforementioned alkyl groups, substituted alkyl groups, and those previously shown as substituents in the substituted alkyl group.

  Preferred examples of such a substituted aryl group include biphenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, fluorophenyl group, chloromethylphenyl group, trifluoromethylphenyl group. Hydroxyphenyl group, methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, Benzoyloxyphenyl group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, cal Xiphenyl group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenylphosphonophenyl Methylphosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonophenyl group, allylphenyl group, 1-propenylmethylphenyl group, 2-butenylphenyl group, 2-methylallylphenyl group, A 2-methylpropenylphenyl group, a 2-propynylphenyl group, a 2-butynylphenyl group, a 3-butynylphenyl group, and the like can be given.

An alkenyl group, a substituted alkenyl group, an alkynyl group, and a substituted alkynyl group (—C (R ⁰² ) ═C (R ⁰³ ) (R ⁰⁴ ) and —C≡C (R ⁰⁵ )) include R ⁰² , R ⁰³ , R ⁰⁴ , and R ⁰⁵ may be a group composed of a monovalent nonmetallic atomic group. Preferable examples of R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ include a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group and a substituted aryl group. Specific examples thereof include those shown as the above-mentioned examples. More preferred groups of R ⁰² , R ⁰³ , R ⁰⁴ , and R ⁰⁵ include a hydrogen atom, a halogen atom, and a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms.

Preferable specific examples of such alkenyl group, substituted alkenyl group, alkynyl group and substituted alkynyl group include vinyl group, 1-propenyl group, 1-butenyl group, 1-pentenyl group, 1-hexenyl group and 1-octenyl group. 1-methyl-1-propenyl group, 2-methyl-1-propenyl group, 2-methyl-1-butenyl group, 2-phenyl-1-ethenyl group, 2-chloro-1-ethenyl group, ethynyl group, 1 -A propynyl group, a 1-butynyl group, and a phenylethynyl group can be mentioned.
Examples of the heterocyclic group include the pyridyl group exemplified as the substituent of the substituted alkyl group.

As the substituted oxy group (R ⁰⁶ O—), a group in which R ⁰⁶ is a group composed of a monovalent nonmetallic atomic group excluding a hydrogen atom can be used. Preferred substituted oxy groups include alkoxy groups, aryloxy groups, acyloxy groups, carbamoyloxy groups, N-alkylcarbamoyloxy groups, N-arylcarbamoyloxy groups, N, N-dialkylcarbamoyloxy groups, N, N-diarylcarbamoyloxy groups. Groups, N-alkyl-N-arylcarbamoyloxy groups, alkylsulfoxy groups, arylsulfoxy groups, phosphonooxy groups, and phosphonatoxy groups. Examples of the alkyl group and aryl group in these include the alkyl groups, substituted alkyl groups, aryl groups, and substituted aryl groups described above. Examples of the acyl group (R ⁰⁷ CO—) in the acyloxy group include those in which R ⁰⁷ is an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group mentioned as the previous example. Among these substituents, an alkoxy group, an aryloxy group, an acyloxy group, and an arylsulfoxy group are more preferable. Specific examples of preferred substituted oxy groups include methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, pentyloxy, hexyloxy, dodecyloxy, benzyloxy, allyloxy, phenethyloxy, Carboxyethyloxy group, methoxycarbonylethyloxy group, ethoxycarbonylethyloxy group, methoxyethoxy group, phenoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, morpholinoethoxy group, morpholinopropyloxy group, allyloxyethoxyethoxy group, Phenoxy group, tolyloxy group, xylyloxy group, mesityloxy group, mesityloxy group, cumenyloxy group, methoxyphenyloxy group, ethoxyphenyloxy group, chlorophenyl Alkoxy group, bromophenyl group, acetyloxy group, benzoyloxy group, naphthyloxy group, a phenylsulfonyloxy group, a phosphonooxy group, phosphonatoxy group, and the like.

The substituted amino group (R ⁰⁸ NH—, (R ⁰⁹ ) (R ⁰¹⁰ ) N—) including an amide group is a group in which R ⁰⁸ , R ⁰⁹ , and R ⁰¹⁰ are monovalent nonmetallic atomic groups excluding hydrogen atoms Can be used. R ⁰⁹ and R ⁰¹⁰ may combine to form a ring. Preferred examples of the substituted amino group include an N-alkylamino group, an N, N-dialkylamino group, an N-arylamino group, an N, N-diarylamino group, an N-alkyl-N-arylamino group, an acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkylureido group, N′-arylureido group, N ′, N′-diarylureido group N′-alkyl-N′-arylureido group, N-alkylureido group, N-arylureido group, N′-alkyl-N-alkylureido group, N′-alkyl-N-arylureido group, N ′, N′-dialkyl-N-alkylureido group, N′-alkyl-N′-arylureido group, N ′, N′-dialkyl-N-alkylureido group, N ′, '-Dialkyl-N'-arylureido group, N'-aryl-N-alkylureido group, N'-aryl-N-arylureido group, N', N'-diaryl-N-alkylureido group, N ', N′-diaryl-N-arylureido group, N′-alkyl-N′-aryl-N-alkylureido group, N′-alkyl-N′-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxy A carbonylamino group, an N-alkyl-N-alkoxycarbonylamino group, an N-alkyl-N-aryloxycarbonylamino group, an N-aryl-N-alkoxycarbonylamino group, and an N-aryl-N-aryloxycarbonylamino group. Can be mentioned. Examples of the alkyl group and aryl group include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group, such as acylamino group, N-alkylacylamino group, and N-arylacylamino. R ⁰⁷ groups definitive acyl group (R ⁰⁷ CO-) are as described above. Of these, more preferred are an N-alkylamino group, an N, N-dialkylamino group, an N-arylamino group, and an acylamino group. Specific examples of preferred substituted amino groups include methylamino group, ethylamino group, diethylamino group, morpholino group, piperidino group, pyrrolidino group, phenylamino group, benzoylamino group, acetylamino group and the like.

As the substituted sulfonyl group (R ⁰¹¹ —SO ₂ —), those in which R ⁰¹¹ is a group composed of a monovalent nonmetallic atomic group can be used. More preferable examples include an alkylsulfonyl group and an arylsulfonyl group. Examples of the alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group. Specific examples of such a substituted sulfonyl group include a butylsulfonyl group, a phenylsulfonyl group, a chlorophenylsulfonyl group, and the like.

As described above, the sulfonate group (—SO ₃ —) means a conjugate base anion group of the sulfo group (—SO ₃ H), and is usually preferably used together with a counter cation. Examples of such counter cations include those generally known, that is, various oniums (ammonium compounds, sulfonium compounds, phosphonium compounds, iodonium compounds, azinium compounds, etc.), and metal ions (Na ⁺ , K +, Ca ^{2). +} , Zn ^2+, etc.).

As the substituted carbonyl group (R ⁰¹³ —CO—), those in which R ⁰¹³ is a group composed of a monovalent nonmetallic atomic group can be used. Preferred examples of the substituted carbonyl group include formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N′-arylcarbamoyl group may be mentioned. Examples of the alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group. Among these, more preferred substituted carbonyl groups include formyl, acyl, carboxyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, N-alkylcarbamoyl, N, N-dialkylcarbamoyl, N-ary. A rucarbamoyl group can be mentioned, and even more preferred are a formyl group, an acyl group, an alkoxycarbonyl group and an aryloxycarbonyl group. Specific examples of preferred substituted carbonyl groups include formyl group, acetyl group, benzoyl group, carboxyl group, methoxycarbonyl group, ethoxycarbonyl group, allyloxycarbonyl group, dimethylaminophenylethenylcarbonyl group, methoxycarbonylmethoxycarbonyl group, N -Methylcarbamoyl group, N-phenylcarbamoyl group, N, N-diethylcarbamoyl group, morpholinocarbonyl group and the like.

As the substituted sulfinyl group (R ⁰¹⁴ —SO—), those in which R ⁰¹⁴ is a group composed of a monovalent nonmetallic atomic group can be used. Preferable examples include alkylsulfinyl group, arylsulfinyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl. Group, N-alkyl-N-arylsulfinamoyl group. Examples of the alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group. Of these, more preferred examples include an alkylsulfinyl group and an arylsulfinyl group. Specific examples of such a substituted sulfinyl group include a hexylsulfinyl group, a benzylsulfinyl group, and a tolylsulfinyl group.

  The substituted phosphono group means a group in which one or two hydroxyl groups on the phosphono group are substituted with other organic oxo groups, and preferred examples thereof include the above-mentioned dialkylphosphono group, diarylphosphono group, alkylarylphospho group. Group, monoalkylphosphono group and monoarylphosphono group. Of these, dialkylphosphono groups and diarylphosphono groups are more preferred. Specific examples thereof include a diethyl phosphono group, a dibutyl phosphono group, a diphenyl phosphono group, and the like.

Phosphonato group _{(-PO 3 H 2 -, -} PO 3 H-) as described above and, phosphono group (-PO ₃ H _2), acid first dissociation or conjugate base anion derived from the second dissociation acid Means group. Usually, it is preferable to use it with a counter cation. Such counter cations include those generally known, that is, various oniums (ammonium, sulfonium, phosphonium, iodonium, azinium, etc.), and metal ions (Na ⁺ , K ⁺ , Ca ²⁺ , Zn ²⁺ etc.).

The substituted phosphonato group is a conjugated base anion group obtained by substituting one organic oxo group in the above-described substituted phosphono group. As a specific example, the above-described monoalkylphosphono group (—PO ₃ H ( alkyl)), and a conjugate base of a monoarylphosphono group (—PO ₃ H (aryl)).

Next, X in the general formula (1) will be described. X is —O—, —S—, —SO ₂ —, —NH—, —N (R ³ ) —, —CH ₂ —, —CH (R ⁴ ) — and —C (R ⁴ ) (R ⁵ ) - represents a divalent linking group selected from, among others, -NH -, - N (R 3) -, - CH 2 -, - CH (R 4) -, - C (R 4) (R 5 ) - preferably from the viewpoint of sensitivity, -NH -, - N (R 3) - more preferably, -N (R ³⁾ - is most preferable in terms of sensitivity and storage stability is.

Here, R ³ , R ⁴ and R ⁵ in X each independently represent a hydrogen atom or a monovalent substituent. Examples of such a monovalent substituent include R ¹ in the general formula (1). , R ² .
In particular, R ³ is preferably an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, each of which may have a substituent. R ³ preferably has at least one of —CO ₂ — and —CON (R ⁸ ) — in its structure, and the most preferable structure of R ³ is represented by the following formula. Is.

In the above formula, R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom or a monovalent substituent, and Z represents a monovalent substituent. Such a monovalent substituent has the same meaning as R ¹ or R ² in the general formula (1).

Further, the monovalent substituent represented by R ⁴ and R ⁵ in X is the same as R ¹ or R ² in the general formula (1).

  Hereinafter, although the specific example (A-1)-(A-87) of the monocarboxylic acid compound represented by General formula (1) is given, this invention is not limited to these.

Next, although the typical synthesis example of the monocarboxylic acid compound which concerns on this invention is shown, this invention is not limited to these.
<Synthesis of Compound (A-24)>
Under a nitrogen stream, 62.8 g of N-phenyliminodiacetic acid was placed in a 2 L eggplant-shaped flask and dissolved in 500 mL of toluene. 32.0 g of acetic anhydride was added, heated to reflux and stirred. After 1 hour, after cooling to room temperature, 3 L of hexane was added with precipitation to cause precipitation. Filtration gave 52.0 g of N-phenyliminodiacetic anhydride.
Next, 5.1 g of the N-phenyliminodiacetic anhydride obtained above was placed in a 200 mL eggplant-shaped flask under a nitrogen stream, and 60 mL of methanol was added. After stirring at room temperature for 6 hours, the solvent was distilled off under reduced pressure. The residue was purified by silica gel chromatography (elution solvent hexane / ethyl acetate) to obtain 5.7 g of compound (A-24). It was confirmed from the NMR spectrum, IR spectrum, and mass spectrometry spectrum that it was the compound (A-24).

<Synthesis of Compound (A-52)>
Under a nitrogen stream, 62.8 g of N-phenyliminodiacetic acid was placed in a 2 L eggplant-shaped flask and dissolved in 500 mL of toluene. 32.0 g of acetic anhydride was added, heated to reflux and stirred. After 1 hour, after cooling to room temperature, 3 L of hexane was added with precipitation to cause precipitation. Filtration gave 52.0 g of N-phenyliminodiacetic anhydride.
Under a nitrogen stream, 5.1 g of the N-phenyliminodiacetic anhydride obtained above was placed in a 200 mL eggplant-shaped flask, and 50 mL of benzyl alcohol was added. After stirring at room temperature for 8 hours, the solvent was distilled off under reduced pressure. The residue was purified by silica gel chromatography (elution solvent hexane / ethyl acetate) to obtain 7.2 g of compound (A-52). It was confirmed from the NMR spectrum, IR spectrum and mass spectrometry spectrum that it was the compound (A-52).

<Synthesis of Compound (A-55)>
Under a nitrogen stream, 62.8 g of N-phenyliminodiacetic acid was placed in a 2 L eggplant-shaped flask and dissolved in 500 mL of toluene. 32.0 g of acetic anhydride was added, heated to reflux and stirred. After 1 hour, after cooling to room temperature, 3 L of hexane was added with precipitation to cause precipitation. Filtration gave 52.0 g of N-phenyliminodiacetic anhydride.
Under a nitrogen stream, 5.1 g of the N-phenyliminodiacetic anhydride obtained above was placed in a 200 mL eggplant-shaped flask, and 50 mL of 1-methoxy-2-propanol was added. After stirring at room temperature for 4 hours, the solvent was distilled off under reduced pressure. The residue was purified by silica gel chromatography (elution solvent hexane / ethyl acetate) to obtain 6.0 g of compound (A-55). It was confirmed from the NMR spectrum, IR spectrum, and mass spectrometry spectrum that it was the compound (A-55).

  The monocarboxylic acid compound according to the present invention described above may be used alone or in combination of two or more. The addition amount of these monocarboxylic acids is 0.1 to 70% by mass, preferably 0.5 to 50% by mass, more preferably 1 to 30% by mass in the total solid content of the polymerizable composition. can do. When the addition amount is within this range, the polymerizable composition of the present invention can provide a sufficient sensitivity improvement effect, and when this polymerizable composition is used as a recording material for a lithographic printing plate precursor, in the non-image area. Occurrence of contamination is suppressed, and excellent film properties can be obtained both before and after the recording layer is cured.

[(F) Other ingredients]
In the polymerizable composition of the present invention, other components suitable for its use, production method and the like can be added as appropriate. In particular, additives that are suitable when the polymerizable composition of the present invention is used as a recording layer of a lithographic printing plate precursor will be described below.

(F-1) Co-sensitizer The sensitivity can be further improved by using a certain additive in the polymerizable composition. Such a compound is hereinafter referred to as a co-sensitizer. These mechanisms of action are not clear, but many are thought to be based on the following chemical processes. That is, a co-sensitizer reacts with various intermediate active species (radicals and cations) generated in the course of the photoreaction initiated by the polymerization initiator and the subsequent addition polymerization reaction to generate new active radicals. Estimated. These can be broadly divided into (i) those that can be reduced to produce active radicals, (ii) those that can be oxidized to produce active radicals, and (iii) radicals that are more active by reacting with less active radicals. Can be classified into those that act as chain transfer agents, but there is often no generality as to which of these individual compounds belong.

(I) Compound that is reduced to generate an active radical Compound having a carbon-halogen bond: It is considered that an active radical is generated by reductive cleavage of the carbon-halogen bond. Specifically, for example, trihalomethyl-s-triazines and trihalomethyloxadiazoles can be preferably used.
Compound having nitrogen-nitrogen bond: It is considered that the nitrogen-nitrogen bond is reductively cleaved to generate an active radical. Specifically, hexaarylbiimidazoles and the like are preferably used.
Compound having oxygen-oxygen bond: It is considered that the oxygen-oxygen bond is reductively cleaved to generate an active radical. Specifically, for example, organic peroxides are preferably used.
Onium compounds: It is considered that carbon-hetero bonds and oxygen-nitrogen bonds are reductively cleaved to generate active radicals. Specifically, for example, diaryliodonium salts, triarylsulfonium salts, N-alkoxypyridinium (azinium) salts and the like are preferably used.
Ferrocene and iron arene complexes: An active radical can be reductively generated.

(Ii) Compound that is oxidized to produce an active radical Alkylate complex: It is considered that a carbon-hetero bond is oxidatively cleaved to produce an active radical. Specifically, for example, triarylalkyl borates are preferably used.
Alkylamine compound: It is considered that the C—X bond on carbon adjacent to nitrogen is cleaved by oxidation to generate an active radical. X is preferably a hydrogen atom, a carboxyl group, a trimethylsilyl group, a benzyl group or the like. Specific examples include ethanolamines, N-phenylglycines, N-trimethylsilylmethylanilines, and the like.
Sulfur-containing and tin-containing compounds: those in which the nitrogen atoms of the above-described amines are replaced with sulfur atoms and tin atoms can generate active radicals by the same action. Further, a compound having an SS bond is also known to be sensitized by SS cleavage.

α-Substituted methylcarbonyl compound: An active radical can be generated by oxidative cleavage of the carbonyl-α carbon bond. Moreover, what converted carbonyl into the oxime ether also shows the same effect | action. Specifically, 2-alkyl-1- [4- (alkylthio) phenyl] -2-morpholinopronone-1 and these and a hydroxylamine were reacted, and then N—OH was etherified. Mention may be made of oxime ethers.
Sulfinic acid salts: An active radical can be reductively generated. Specific examples include arylsulfin sodium.

(Iii) Compounds that react with radicals to convert to highly active radicals or act as chain transfer agents: For example, a group of compounds having SH, PH, SiH, GeH in the molecule is used. These can donate hydrogen to low-activity radical species to generate radicals, or can be oxidized and then deprotonated to generate radicals. Specifically, 2-mercaptobenzimidazoles etc. are mentioned, for example.

More specific examples of these (F-1) co-sensitizers are described, for example, in JP-A-9-236913 as additives for the purpose of improving sensitivity. The present invention can also be applied.
These (F-1) cosensitizers can be used alone or in combination of two or more. The amount used is suitably in the range of 0.05 to 100 parts by weight, preferably 1 to 80 parts by weight, more preferably 3 to 50 parts by weight with respect to 100 parts by weight of the polymerizable compound (C).

(F-2) Polymerization inhibitor In the present invention, in order to prevent unnecessary thermal polymerization of the polymerizable compound (C) during the production or storage of the polymerizable composition constituting the recording layer, (F -2) It is desirable to add a small amount of a thermal polymerization inhibitor as a 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 entire composition. In addition, if necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide is added to prevent polymerization inhibition due to oxygen, and a lithographic printing plate precursor is dried after coating on a support or the like. In this process, it may be unevenly distributed on the surface of the recording layer. The amount of the higher fatty acid derivative added is preferably about 0.5% by mass to about 10% by mass of the total composition.

(F-3) Colorant, etc. Furthermore, in the planographic printing plate precursor according to the invention, a dye or pigment may be added for the purpose of coloring the recording layer. Thereby, so-called plate inspection properties such as visibility after plate making and suitability for an image density measuring machine as a printing plate can be improved. As the colorant, many dyes cause a decrease in the sensitivity of the photopolymerization recording 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 of the total composition.

(F-4) Other additives The polymerizable composition of the present invention is described in the specification of Japanese Patent Application No. 2003-058410 filed earlier by the applicant of the present application for the purpose of further improving sensitivity, stability, and developability. It is preferable to add a compound having at least one carboxylic acid group and at least one amino group or thioether group in the molecule.

  Furthermore, the polymerizable composition of the present invention improves the ink depositing property on the surface of the recording layer when used as an inorganic filler for improving the physical properties of the cured film, as well as a plasticizer and a lithographic printing plate precursor. You may add well-known additives, such as a fat-sensitizing agent to obtain.

  Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin, and the like. In this case, 10% by mass or less can be added with respect to the total mass of the compound having an ethylenically unsaturated double bond and the binder.

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.
In addition, it is possible to contain an additive for improving the adhesion between the recording layer and the support, which will be described later, and improving the development removability of the unexposed recording layer. For example, by adding a compound having a relatively strong interaction with the support, such as a compound having a diazonium structure or a phosphone compound, or by undercoating them, it is possible to improve adhesion and improve printing durability. is there. Further, by adding a hydrophilic polymer such as polyacrylic acid or polysulfonic acid, or by undercoating them, the developability of the non-image area is improved, and the stain resistance can be improved.

[Image recording material]
Next, the image recording material of the present invention using the polymerizable composition will be described. In the image recording material of the present invention, the polymerizable composition is used for a recording layer. That is, the recording layer of the image recording material of the present invention comprises (A) a dye having absorption at a wavelength of 700 to 1300 nm, (B) a radical polymerization initiator having an alkali-soluble group, and (C) an ethylenically unsaturated bond. And a compound having Furthermore, it is preferable to add (D) a binder polymer and / or (E) a compound represented by the general formula (1) to the recording layer. In addition, it is preferable to use the polymer containing the structural unit which has an alkali-soluble group represented with the said general formula (I) as this binder polymer.
In this recording layer, (A) an infrared absorber generates heat by irradiation with an infrared laser, and (B) a specific initiator decomposes to generate radicals by the heat, and (C) a compound having an ethylenically unsaturated bond The exposure reaction is accelerated, and the exposed portion is cured to form a negative image that becomes an image portion.
The image recording material of the present invention is preferably used mainly as a lithographic printing plate precursor. The lithographic printing plate precursor, which is a preferred application of the image recording material of the present invention, will be described in detail below.

[Manufacture of lithographic printing plate precursors]
In order to produce a lithographic printing plate precursor according to the present invention, a recording layer coating solution containing the polymerizable composition as a main component is prepared, and other components such as a protective layer are also used as solvents. What is necessary is just to apply | coat to a suitable support body by preparing a coating liquid by melt | dissolving in.
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 are ethyl and the like. 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 recording layer on the support is preferably selected according to the intended use in consideration of the sensitivity of the recording layer, the developability, the strength of the exposed film and the printing durability. 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. In general, the coating amount of the lithographic printing plate precursor according to the present invention is suitably in the range of about 0.1 to about 10 g / m ² in terms of the mass after drying. More preferably from 0.5 to 5 g / m ^2.

(Protective layer)
Since the lithographic printing plate precursor according to the invention is usually exposed in the air, it is preferable to further provide a protective layer on the recording layer. 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 recording layer, and enables exposure in the air. To do. Therefore, the properties desired for such a protective layer are low permeability of low-molecular compounds such as oxygen, furthermore, good transparency of light used for exposure, and excellent adhesion to the recording layer, And it is desirable that it can be easily removed in the development step after exposure.

  Such a device for the protective layer has been conventionally devised, which 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 polyacrylic acid are known, and among these, using 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. In particular, a mixture obtained by replacing polyvinyl pyrrolidone in a range of 15 to 50% by mass with respect to polyvinyl alcohol is preferable from the viewpoint of storage stability.

  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 a new oil-based polymer layer, film peeling due to insufficient adhesion tends 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, in JP-A-49-70702 and British Patent Application No. 1,303,578A, an acrylic emulsion or a water-insoluble vinyl pyrrolidone-vinyl acetate is contained 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 of a copolymer or the like and laminating on a polymerized 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 Japanese Patent Publication No. 55-49729.

  Furthermore, other functions can be imparted to the protective layer. For example, by adding a colorant (such as a water-soluble dye) that excels in the transmission of light of the wavelength used for exposure and that can efficiently absorb light of a wavelength that does not contribute to image formation, safe light does not occur. Suitability can be further enhanced.

Moreover, as a protective layer in the lithographic printing plate precursor according to the present invention, the oxygen permeability described in JP 2000-347398 A is 1 × 10 ⁻¹⁵ {cm ³ (STP) · cm / cm ² · sec · cmHg}. The above protective layer can also be used suitably.

(Resin intermediate layer)
In the lithographic printing plate precursor according to the invention, a resin intermediate layer made of an alkali-soluble polymer can be provided between the recording layer and the support, if necessary.
The recording layer, which is an infrared-sensitive layer whose solubility in an alkaline developer is lowered by exposure, is provided on or near the exposed surface, thereby improving the sensitivity to the infrared laser, and the support and the infrared-sensitive recording. This resin intermediate layer exists between the layers and functions as a heat insulation layer, so that the heat generated by the infrared laser exposure does not diffuse to the support and can be used efficiently so that the sensitivity can be increased. .
In the exposed area, the recording layer that is impermeable to the alkali developer functions as a protective layer for the resin intermediate layer, so that the development stability is good and the image is excellent in discrimination. In the unexposed area, the uncured binder component quickly dissolves and disperses in the developer, and is adjacent to the support. Since this resin intermediate layer is made of an alkali-soluble polymer, the solubility in a developing solution is good. For example, even when a developing solution with reduced activity is used, a residual film or the like is generated. It is considered that it is excellent in developability because it dissolves quickly.

(Support)
The support used for the lithographic printing plate precursor according to the present invention is not particularly limited as long as it is a dimensionally stable plate-like material. For example, paper, plastic (for example, polyethylene, polypropylene, polystyrene, etc.) is used. Laminated paper, metal plate (eg, aluminum, zinc, copper, etc.), plastic film (eg, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, Polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.). These may be a single component sheet such as a resin film or a metal plate, or may be a laminate of two or more materials. For example, a paper or plastic film on which a metal as described above is laminated or vapor-deposited. And laminated sheets of different plastic films.

As the above-mentioned support, a polyester film or an aluminum plate is preferable, and among them, an aluminum plate that has good dimensional stability and is relatively inexpensive is particularly preferable. A suitable aluminum plate is a pure aluminum plate or an alloy plate containing aluminum as a main component and containing a trace amount of different elements, and may be a plastic film on which aluminum is laminated or vapor-deposited. Examples of foreign elements contained in the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, and titanium. The content of foreign elements in the alloy is at most 10% by mass. Particularly suitable aluminum in the present invention is pure aluminum, but completely pure aluminum is difficult to produce in the refining technique, and may contain slightly different elements. Thus, the composition of the aluminum plate applied to the present invention is not specified, and conventionally known and used aluminum plates can be appropriately used.
The thickness of the aluminum plate is about 0.1 to 0.6 mm, preferably 0.15 to 0.4 mm, and particularly preferably 0.2 to 0.3 mm.

Prior to roughening the aluminum plate, a degreasing treatment with, for example, a surfactant, an organic solvent, an alkaline aqueous solution or the like is performed to remove the rolling oil on the surface, if desired.
The surface roughening treatment of the aluminum plate is performed by various methods. For example, a method of mechanically roughening, a method of electrochemically dissolving and roughening a surface, and a method of selectively dissolving a surface chemically. This is done by the method of As the mechanical method, a known method such as a ball polishing method, a brush polishing method, a blast polishing method, or a buff polishing method can be used. Further, as an electrochemical surface roughening method, there is a method of performing alternating current or direct current in hydrochloric acid or nitric acid electrolyte. Further, as disclosed in JP-A-54-63902, a method in which both are combined can also be used.
The aluminum plate roughened in this way can be subjected to an anodizing treatment to enhance the water retention and wear resistance of the surface through an alkali etching treatment and a neutralization treatment, if desired. As the electrolyte used for the anodizing treatment of the aluminum plate, various electrolytes that form a porous oxide film can be used. In general, sulfuric acid, phosphoric acid, oxalic acid, chromic acid, or a mixed acid thereof is used. The concentration of these electrolytes is appropriately determined depending on the type of electrolyte.

The treatment conditions for anodization vary depending on the electrolyte used, and thus cannot be specified in general. However, in general, the electrolyte concentration is 1 to 80% by mass solution, the liquid temperature is 5 to 70 ° C., and the current density is 5 to 60 A / day. dm ² , voltage 1 to 100 V, and electrolysis time 10 seconds to 5 minutes are suitable.
The amount of the anodized film is suitably 1.0 g / m ² or more, but more preferably in the range of 2.0 to 6.0 g / m ^2. When the anodic oxide coating is less than 1.0 g / m ² , the printing durability is insufficient, or the non-image part of the lithographic printing plate is easily scratched, so that the ink adheres to the scratched part during printing. “Scratches and dirt” are likely to occur.
Such an anodic oxidation treatment is applied to the surface used for printing on the support of the lithographic printing plate, but an anodized film of 0.01 to 3 g / m ² is also formed on the back surface due to the back of the lines of electric force. It is common to form.

The hydrophilization treatment of the support surface is performed after the anodizing treatment, and a known treatment method is used. Such hydrophilization treatment is disclosed in US Pat. Nos. 2,714,066, 3,181,461, 3,280,734 and 3,902,734. There is an alkali metal silicate method (for example, sodium silicate aqueous solution). In this method, the support is immersed in an aqueous sodium silicate solution or electrolytically treated. In addition, potassium fluoride zirconate disclosed in Japanese Patent Publication No. 36-22063 and U.S. Pat. Nos. 3,276,868, 4,153,461, and 4,689,272 For example, a method of treating with polyvinylphosphonic acid as disclosed in the document is used.
Among these, a particularly preferred hydrophilic treatment in the present invention is a silicate treatment. The silicate treatment will be described below.

The anodized film of the aluminum plate subjected to the treatment as described above has an alkali metal silicate content of 0.1 to 30% by mass, preferably 0.5 to 10% by mass, and a pH at 25 ° C. of 10 to 13. For example, it is immersed in an aqueous solution at 15 to 80 ° C. for 0.5 to 120 seconds. If the pH of the alkali metal silicate aqueous solution is lower than 10, the solution will gel, and if it is higher than 13.0, the oxide film will be dissolved. Examples of the alkali metal silicate used in the present invention include sodium silicate, potassium silicate, and lithium silicate. Examples of the hydroxide used to increase the pH of the alkali metal silicate aqueous 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 salts such as sulfate, hydrochloride, phosphate, acetate, oxalate, and borate. Can be mentioned. Examples of Group IVB metal salts include titanium tetrachloride, titanium trichloride, potassium titanium fluoride, potassium potassium oxalate, titanium sulfate, titanium tetraiodide, zirconium chloride, zirconium dioxide, zirconium oxychloride, zirconium tetrachloride, etc. Can do. 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.
Since the hydrophilicity on the surface of the aluminum plate is further improved by the silicate treatment, the ink hardly adheres to the non-image area during printing, and the stain performance is improved.

(Back coat layer)
A back coat is provided on the back surface of the support as necessary. As such a backcoat, a coating comprising a metal oxide obtained by hydrolysis and polycondensation of an organic polymer compound described in JP-A-5-45885 and an organic or inorganic metal compound described in JP-A-6-35174 A layer is preferably used.
Among these coating layers, silicon alkoxy compounds such as Si (OCH ₃ ) ₄ , Si (OC ₂ H ₅ ) ₄ , Si (OC ₃ H ₇ ) ₄ , and Si (OC ₄ H ₉ ) ₄ are available at a low price. The coating layer of the metal oxide provided therefrom is particularly preferred because of its excellent development resistance.
As described above, the planographic printing plate precursor according to the invention can be prepared.

[Plate making]
The lithographic printing plate precursor according to the present invention is subjected to image formation (recording) by exposure, and thereafter subjected to development processing described later to make a plate. The polymerization reaction in the polymerizable composition of the present invention is also carried out by exposure.

(exposure)
The image recording material and the polymerizable composition of the present invention are preferably subjected to image exposure with a solid-state laser and a semiconductor laser that emit infrared rays having a wavelength of 760 nm to 1200 nm.
Further, the exposure mechanism may be any of an internal drum system, an external drum system, a flat bed system, and the like.
In the present invention, the development treatment may be performed immediately after the laser irradiation, but the heat treatment may be performed between the laser irradiation step and the development step. It is preferable to perform the conditions of heat processing within the range of 80 to 150 degreeC for 10 second-5 minutes. This heat treatment can reduce the laser energy required for recording during laser irradiation.

(developing)
The lithographic printing plate precursor according to the invention is usually developed with water or an alkaline aqueous solution after image exposure with an infrared laser.
The developer used is preferably an alkaline aqueous solution, and a preferable pH range includes a pH range of 10.5 to 12.5, and further development processing is performed with an alkaline aqueous solution having a pH range of 11.0 to 12.5. preferable. If an alkaline aqueous solution having a pH of less than 10.5 is used, the non-image area tends to be smeared, and development with an aqueous solution having a pH of more than 12.5 may reduce the strength of the image area.

When an alkaline aqueous solution is used as the developer, a conventionally known alkaline aqueous solution can be used as the developer and replenisher used in the lithographic printing plate precursor according to the invention. For example, sodium silicate, potassium, tribasic sodium phosphate, potassium, ammonium, dibasic sodium phosphate, potassium, ammonium, sodium carbonate, potassium, ammonium, sodium bicarbonate, potassium, Examples include inorganic alkali salts such as ammonium, sodium borate, 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.

  Furthermore, when developing using an automatic developing machine, the developer in the developing tank can be developed for a long time by adding an aqueous solution (replenisher) that is the same as the developer or having a higher alkali strength than the developer to the developer. It is known that a large amount of a lithographic printing plate precursor can be processed without changing the liquid. This replenishment method is also preferably applied in the present invention.

Various surfactants, organic solvents, and the like can be added to the developer and the replenisher as necessary for the purpose of promoting and suppressing developability, dispersing development residue, and improving the ink affinity of the printing plate image area.
It is preferable to add 1 to 20% by mass of a surfactant in the developer, and more preferably in the range of 3 to 10% by mass. When the addition amount is within this range, such a lithographic printing plate precursor can obtain a sufficient effect of improving developability, and there is no concern that the strength such as abrasion resistance of the image is lowered.
Preferred surfactants include anionic, cationic, nonionic and amphoteric surfactants. Specifically, for example, sodium salt of lauryl alcohol sulfate, ammonium salt of lauryl alcohol sulfate, sodium salt of octyl alcohol sulfate, for example, sodium salt of isopropyl naphthalene sulfonic acid, sodium salt of isobutyl naphthalene sulfonic acid, polyoxyethylene glycol Higher alcohols having 8 to 22 carbon atoms such as sodium salt of mononaphthylethyl sulfate, sodium salt of dodene benzene sulfonic acid, alkyl aryl sulfonate such as sodium salt of metanitrobenzene sulfonic acid, secondary sodium alkyl sulfate, etc. sulfates, fatty alcohol phosphoric acid ester salts such as sodium salt of cetyl alcohol phosphate esters, e.g., C ₁₇ H ₃₃ CON ( _{H 3) CH 2 CH 2 SO} 3 sulfonates of alkylamides such as Na, for example, sodium dioctylsulfosuccinate, sodium sulfo sulfonates of dibasic aliphatic esters such as succinic acid dihexyl ester, for example, lauryl Ammonium salts such as trimethylammonium chloride, lauryltrimethylammonium methosulfate, for example amine salts such as stearamide ethyl diethylamine acetate, polyhydric alcohols such as fatty acid monoester of glycerol, fatty acid monoester of pentaerythritol, for example, Examples include polyethylene glycol ethyls such as polyethylene glycol mononaphthyl ethyl and polyethylene glycol mono (noelphenol) ethyl.

  Preferred organic solvents include those having a solubility in water of about 10% by mass or less, and more preferably those having a solubility in water of 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 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 surfactant is small, the organic solvent is not dissolved, and therefore it is impossible to expect good developability.

Furthermore, the developer and replenisher may contain additives such as an antifoaming agent and a hard water softening agent as necessary. The water softeners, _{e.g., Na 2 P 2 O 7,} Na 5 P 3 O 3, Na 3 P 3 O 3, Na 2 O 4 P (NaO 3 P) ΡO 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. May be contained in the range of 0.01 to 0.5% by mass.

  Further, when developing the lithographic printing plate using an automatic developing machine, the developing solution becomes fatigued according to the amount of processing. Therefore, the processing capacity can be recovered by using a replenishing solution or a fresh developing solution. Also good. In this case, it is preferable to replenish by the method described in US Pat. No. 4,882,246.

  Examples of the developer containing such a surfactant, an organic solvent and a reducing agent include benzyl alcohol, anionic surfactant, alkali agent and water described in JP-A No. 51-77401. A developer composition comprising: an aqueous solution containing benzyl alcohol, an anionic surfactant, and a water-soluble sulfite described in JP-A-53-44202; -155355, a developer composition containing an organic solvent having a solubility in water of 10% by mass or less at normal temperature, an alkaline agent, and water, and the like, and is also preferably used in the present invention. The

  The lithographic printing plate developed using the developer and replenisher described above is post-treated with a desensitizing solution containing rinsing solution containing a washing water, a surfactant and the like, gum arabic and starch derivatives. As the post-treatment of the planographic printing plate of the present invention, these treatments can be used in various combinations.

In recent years, automatic developing machines for printing plate materials have been widely used in the plate making and printing industries in order to rationalize and standardize plate making operations. This automatic developing machine is generally composed of a developing unit and a post-processing unit, and includes an apparatus for conveying a printing plate material, processing liquid tanks and a spray device. Each processing liquid pumped up is sprayed from a spray nozzle for development processing. Further, recently, a method is also known in which a printing plate precursor is immersed and conveyed in a processing liquid tank filled with a processing liquid by a submerged guide roll or the like. In such automatic processing, each processing solution can be processed while being supplemented with a replenisher according to the processing amount, operating time, and the like. In addition, the electrical conductivity can be detected by a sensor and replenished automatically.
In addition, a so-called disposable processing method in which processing is performed with a substantially unused processing solution can also be applied.

The lithographic printing plate obtained as described above can be subjected to a printing process after applying a desensitized gum if desired. However, if it is desired to obtain a lithographic printing plate with higher printing durability, Processing is performed.
In the case of burning a lithographic printing plate, before burning, an adjustment as described in JP-B-61-2518, JP-A-55-28062, JP-A-62-31859, JP-A-61-159655 is used. It is preferable to treat with a surface liquid.
As its method, with a sponge or absorbent cotton soaked with the surface-adjusting liquid, it is applied onto a lithographic printing plate, or a method in which the printing plate is immersed and applied in a vat filled with the surface-adjusting liquid, Application by an automatic coater is applied. Further, it is more preferable to make the coating amount uniform with a squeegee or a squeegee roller after coating.

The lithographic printing plate subjected to the burning treatment can be subjected to conventional treatments such as washing and gumming as needed, but a surface-conditioning solution containing a water-soluble polymer compound is used. In such a case, so-called desensitizing treatment such as gumming can be omitted.
The lithographic printing plate obtained by such treatment is applied to an offset printing machine or the like and can be used for printing a large number of sheets.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

[Examples 1 to 11, Comparative Examples 1 and 2]
[Production of substrate]
A 0.3 mm thick aluminum plate (material 1050) was washed with trichlorethylene and degreased, then this surface was etched using a nylon brush and a 400 mesh pumice-water suspension, washed with water, and further washed. It was immersed in 20% nitric acid for 20 seconds and washed with water. The etching amount of the grained surface at this time was about 3 g / m ² .
Next, this plate was provided with a DC electrode oxide film having a current density of 15 A / dm ² and 3 g / m ² using 7% sulfuric acid as an electrolytic solution, then washed with water and dried to prepare a substrate [A].
Substrate [A] was treated with a 2 wt% aqueous solution of sodium silicate at 25 ° C. for 15 seconds and washed with water to prepare substrate [B].

[Formation of intermediate layer]
Next, a SG method liquid composition (sol solution) was prepared by the following procedure.
<Sol solution composition>
・ Methanol 130g
・ Water 20g
・ 85% phosphoric acid 16g
・ Tetraethoxysilane 50g
・ 60 g of 3-methacryloxypropyltrimethoxysilane

The above compounds were mixed and stirred. An exotherm was observed in about 5 minutes. After reacting for 60 minutes, the contents were transferred to another container, and 3000 g of methanol was added to obtain a sol solution.
This sol solution is diluted with methanol / ethylene glycol = 9/1 (weight ratio) so that the amount of Si on the substrate is 3 mg / m ² on the substrate [A] produced as described above. It apply | coated and dried at 100 degreeC for 1 minute, and board | substrate [C] was obtained.

[Formation of planographic printing plate precursor]
One of the substrates [A] to [C] prepared as described above is used as a support, a recording layer coating solution having the following composition is applied to the surface, dried at 120 ° C. for 1 minute, and 1.4 g / An m ² photosensitive layer was formed to obtain a lithographic printing plate precursor.

<Recording layer coating solution>
-(A) Infrared absorber (compound described in Table 1) 0.085 g
-Radical polymerization initiator (compound described in Table 1) 0.23 g
(In the examples, it corresponds to the component (B))
-(C) Polymerizable compound (compound described in Table 1) 1.00 g
-(D) Binder polymer (compound described in Table 1) 1.05 g
・ (E) Monocarboxylic acid compound 0.07g
(Compounds listed in Table 1, but added only in Examples 9-11)
・ Fluorine nonionic surfactant 0.025g
(F-177P, manufactured by Dainippon Ink & Chemicals, Inc.)
・ Ethyl violet-6Hnaps 0.040g
・ Methyl ethyl ketone 9g
・ 10 g of 1-methoxy-2-propanol
・ Methanol 5g

  In addition, the radical polymerization initiator used in Examples 1-11 is (B) specific initiator which is the characteristic component of this invention, and the radical polymerization initiator used in Comparative Examples 1 and 2 is the thing of this invention. It is a radical polymerization initiator outside the range. The structures of radical polymerization initiators (H-1) and (H-2) are shown below as comparative examples.

  The structures of (A) infrared absorbers (IR-1) to (IR-3) used in the examples of the present invention are shown below.

(C) The polymerizable compounds (M-1) and (M-2) used in the examples of the present invention are as follows.
(M-1): Shin Nakamura Chemical Co., Ltd. NK ester A-BPE-4
(M-2): KAYARAD D-310 manufactured by Nippon Kayaku Co., Ltd.

The structures of (D) binder polymers (P-1) and (P-2) used in the examples of the present invention are shown below. (P-3) is a polyurethane resin which is a condensate of diisocyanate and diol of the following (a) to (d).
(A) 4,4′-diphenylmethane diisocyanate (b) hexamethylene diisocyanate (c) polypropylene glycol (weight average molecular weight: 1000)
(D) 2,2-bis (hydroxymethyl) propionic acid (copolymerization molar ratio: a / b / c / d = 40/10/15/35)

  The structures of (E) monocarboxylic acid compounds (E-1) and (E-2) used in the examples of the present invention are shown below.

[Formation of protective layer]
A 3% by mass aqueous solution of polyvinyl alcohol (degree of saponification: 98 mol%, degree of polymerization: 550) was applied on the recording layer formed as described above so that the application amount after drying was 2 g / m ^2. And dried at 100 ° C. for 1 minute to provide a protective layer.
As described above, lithographic printing plate precursors of Examples 1 to 11 and Comparative Examples 1 and 2 were obtained.

[Evaluation of developability variation with forced aging]
The lithographic printing plate precursors of Examples 1 to 11 and Comparative Examples 1 and 2 thus obtained were exposed using a Trend setter 3244VX manufactured by Creo equipped with a water-cooled 40 W infrared semiconductor laser with an output of 4 W and an outer drum rotating speed of 120 revolutions. did. Next, it is immersed in a developer at 35 ° C. (DV-2 developer / water = 1/4 manufactured by Fuji Photo Film Co., Ltd.) until the residual color ratio of the developing part (non-image part) becomes 3% or less. The development time was determined.
Subsequently, the same lithographic printing plate precursor was allowed to stand for 70 hours at a forced aging condition, 75% humidity, and 40 ° C., and then exposed and developed under the same conditions as in the evaluation of the developability. Thus, the development time required until the remaining color ratio of the developing portion (non-image portion) became 3% or less was obtained.
The remaining color ratio of the non-image area was measured by the cyan density of Spectrodensitometer manufactured by X-Rite.

  The development time of the lithographic printing plate precursor not subjected to forced aging was compared with the development time of the lithographic printing plate precursor after forced aging, and the difference was determined. The smaller the development time difference with and without forced aging, the smaller the change in developability with time. 5 seconds or less is effective. The results are also shown in Table 1.

[Evaluation of Discrimination]
The lithographic printing plate precursors of Examples 1 to 11 and Comparative Examples 1 and 2 were exposed under the same conditions as described above, and a developer at 35 ° C. (DV-2 developer / water = 1/4 manufactured by Fuji Photo Film Co., Ltd.) And developed for 30 seconds to obtain a lithographic printing plate.
Subsequently, the image part and the non-image part were measured by X-Rite Co. and Spectrodensitometer cyan density, respectively.
The plate without the recording layer applied and the plate with the recording layer applied before development were measured by the cyan density, and the density difference was taken as 100% to determine the difference between the exposed and developed image area and non-image area. Concentration differences were compared. 96% or more is considered good. The results are also shown in Table 1.

[Evaluation of printing durability]
The lithographic printing plate precursors of Examples 1 to 11 and Comparative Examples 1 and 2 were exposed under the same conditions as in the evaluation of the developability, and using the same developer, the residual color rate (in the same manner as described above) Development was carried out while changing the time so that (measurement) was 3% or less.
Next, Value-G ink N manufactured by Dainippon Ink & Chemicals, Inc. was used as the ink on a Lithlon 40 printing machine manufactured by Komori Corporation, and IF manufactured by Fuji Photo Film Co., Ltd. as the dampening water component. Printing was performed using 4% of -102. In Comparative Example 1, the relative number of the lithographic printing plates of Examples 1 to 11 and Comparative Example 2 was determined, assuming that the number of images obtained by visually observing a clear image without blurring or white spots was 100. The results are also shown in Table 1.

From the results shown in Table 1, the lithographic printing plate precursors of Examples 1 to 11 of the present invention have lower developability over time even when stored in a severe atmosphere such as high temperature and high humidity as compared with Comparative Examples 1 and 2. This was found to be excellent in discrimination and printing durability.
In addition, the lithographic printing plate precursors of Examples 9 to 11 to which (E) the monocarboxylic acid compound was added were more stable than the other examples to which the component (E) was not added. It was confirmed that the printing durability was improved.

Claims (8)

(A) a dye having absorption at a wavelength of 700 to 1300 nm;
(B) a radical polymerization initiator having an alkali-soluble group;
(C) a compound having an ethylenically unsaturated bond;
A polymerizable composition comprising: (B) The polymerizable composition according to claim 1, wherein the radical polymerization initiator having an alkali-soluble group has an onium salt structure. The polymerizable composition according to claim 1, further comprising (D) a binder polymer. The polymerizable composition according to claim 3, wherein (D) the binder polymer has a structural unit represented by the following general formula (I).

(In General Formula (I), R ¹ represents a hydrogen atom or a methyl group, and R ² represents one or more atoms selected from the group consisting of a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom. The number of atoms excluding the substituent is 2 to 30. A represents an oxygen atom or —NR ³ —, and R ³ represents a hydrogen atom or a monovalent group having 1 to 10 carbon atoms. And n represents an integer of 1 to 5.) Furthermore, (E) The compound represented by following General formula (1) is contained, The polymeric composition of any one of Claim 1 thru | or 4 characterized by the above-mentioned.

(In the formula (1), A is the respective .R ¹ or R ² represents an aromatic group or a heterocyclic group independently represents a hydrogen atom or a monovalent substituent. In addition, R ¹ and R ^2, R ¹ and R ² and X, R ¹ and R ² and A, A and X may be bonded to each other to form a ring structure, where X is —O—, —S—, —SO ₂ —. , -NH -, - N (R 3) -, - CH 2 -, - CH (R 4) -, and ^{-C (R 4) (R 5} ) - represents a divalent linking group selected from, R ³ , R ⁴ and R ⁵ each independently represents a hydrogen atom or a monovalent substituent.) (B) The polymerizable composition according to any one of claims 1 to 5, wherein the radical polymerization initiator having an alkali-soluble group is a sulfonium salt. (B) The polymerizable compound according to any one of claims 1 to 6, wherein the radical polymerization initiator having an alkali-soluble group is a sulfonium salt composed of a sulfonium cation and a sulfonate anion. An image recording material having a recording layer containing the polymerizable composition according to any one of claims 1 to 7 on a support.