JP2005208133A - Photopolymerizable lithographic printing plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photopolymerizable lithographic printing plate having high sensitivity and ensuring good storage stability while maintaining handling property in a bright room. <P>SOLUTION: The lithographic printing plate satisfies a relationship of an expression (1), X<SB>0</SB>(%)-5≤X<SB>10</SB>(%) between the average X<SB>10</SB>of dot areas of 20%, 30%, 40% and 50% measured after a forced time lapse test in which the lithographic printing plate is stored under a forced storage condition of 60°C for 10 days, and the average X<SB>0</SB>of dot areas of 20%, 30%, 40% and 50% measured before the forced time lapse test. The lithographic printing plate is obtained by disposing on a support a photopolymerizable photosensitive layer containing: (A) a sensitizing dye; (B) an activator compound which causes a chemical change by interaction with an electron excited state produced by light absorption of the sensitizing dye and generates a radical or an acid; (C) an addition polymerizable compound which reacts under at least any of a radical or an acid; and (D) a plasticizer. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a photopolymerizable lithographic printing plate, and more particularly, to a photopolymerizable lithographic printing plate having high sensitivity, good storage stability and good room handling.

In the field of photosensitive lithographic printing plate precursors, solid lasers, semiconductor lasers, and gas lasers that emit ultraviolet light, visible light, and infrared light having a wavelength of 300 nm to 1200 nm are easily available in high output and small size. These lasers are very useful as a recording light source when directly making a plate from digital data of a computer or the like.
Various studies have been made on lithographic printing plate precursors (hereinafter also referred to simply as recording materials) that are sensitive to these various laser beams. As a typical example, recording can be performed with an infrared laser having a photosensitive wavelength of 760 nm or more. Examples of the material include a positive recording material described in Patent Document 1 (US Pat. No. 4,708,925), an acid-catalyzed crosslinking negative recording material described in Patent Document 2 (Japanese Patent Laid-Open No. 8-276558), and the like. Second, recording materials compatible with 300 nm to 700 nm ultraviolet light or visible light laser are described in Patent Document 3 (US Pat. No. 2,850,445) and Patent Document 4 (Japanese Patent Publication No. 44-20189). There is a radical polymerization type negative recording material.

Among them, the radical photopolymerization type has high sensitivity, and is advantageous for a so-called direct printing plate in which imagewise exposure is performed directly on a plate without using a conventional lith film by various lasers from a computer.
In the field of the direct printing plate, a combination of a visible light laser light source of 488 nm and 532 nm and a photopolymerization planographic printing plate has already been put into practical use. In order to cope with an improvement in drawing speed as a pursuit of higher productivity. In addition to the need for higher sensitivity, there is an increasing demand for handling (under a bright room) under a yellow or white light instead of a dark room in terms of workability.

Furthermore, a photopolymerization initiator or a photopolymerization initiation system has been designed and developed for the purpose of increasing the sensitivity, and various compounds are used. In addition, a photosensitive composition containing a photopolymerization initiating system that does not absorb in the visible light region or very little has been designed, such as an ultraviolet-violet laser having a wavelength of 300 nm to 450 nm and an infrared laser having a wavelength of 800 to 1200 nm. A bright room is also possible by combining with the exposure method.
A highly sensitive photopolymerizable composition basically contains an ethylenically unsaturated compound, a photopolymerization initiating system, and a binder resin, and in image formation, the photoinitiating system absorbs light and generates active radicals to produce ethylene. This causes addition polymerization of the unsaturated compound and insolubilization of the photosensitive layer. Most of the conventional proposals relating to the photopolymerizable composition capable of scanning exposure disclose the use of a photoinitiating system excellent in photosensitivity. For example, Patent Document 5 (Bruce M. Monroe et al., Chemical Revue, 93, 435 (1993)) and Patent Document 6 (RS Davidson, Journal of Photochemistry and biology A: Chemistry, 73, 81 (1993)).

However, a photosensitive layer containing such a high-sensitivity photopolymerization initiation system is difficult to achieve both sensitivity and storage stability, the sensitivity decreases during long-term storage at room temperature, and there is concern about reproducibility during printing. It was.
U.S. Pat. No. 4,708,925 JP-A-8-276558 U.S. Pat. No. 2,850,445 Japanese Patent Publication No. 44-20189 Bruce M. Monroe et al., Chemical Revue, 93, 435 (1993) RS Davidson, Journal of Photochemistry and biology A: Chemistry, 73, 81 (1993)

  Accordingly, the present invention is intended to overcome the above problems and provide a photopolymerizable lithographic printing plate having high sensitivity and good storage stability while maintaining bright room handling.

As a result of intensive studies, the present inventors have made it possible to achieve both sensitivity and storage stability by adding a plasticizer as a photosensitive layer component, particularly in a plasticizer having at least four ester groups, the storage stability effect thereof. Found that it was great.
That is, the present invention has the following configuration.
(1) An average value X _{10 of} 20%, 30%, 40%, and 50% halftone dot area measured after a forced aging test stored for 10 days under a forced storage condition at 60 ° C., and measured before the forced aging test The lithographic printing plate is characterized in that the relationship of the average value X ₀ of the halftone dot areas of 20%, 30%, 40% and 50% is expressed by the formula (1).
X ₀ (%) − 5 ≦ X ₁₀ (%) (1)

(2) On the support, (A) a sensitizing dye, (B) an activator compound that undergoes a chemical change by interaction with an electronically excited state caused by light absorption of the sensitizing dye, and generates a radical or an acid; A lithographic printing plate precursor comprising a photopolymerizable photosensitive layer containing C) an addition polymerizable compound that reacts with at least one of a radical and an acid, and (D) a plasticizer.
(3) The lithographic printing plate as described in (2) above, wherein the plasticizer is a compound having at least 4 ester groups.

  According to the present invention, it is possible to provide a photopolymerizable lithographic printing plate having high sensitivity and good storage stability and light room handling.

Embodiments of the present invention will be described in detail.
The lithographic printing plate of the present invention generates a radical or an acid on a support by causing a chemical change by interaction with (A) a sensitizing dye and (B) an electronically excited state caused by light absorption of the sensitizing dye. An activator compound, (C) an addition polymerizable compound that reacts with at least one of a radical and an acid, and (D) a plasticizer as an essential component, and further contains (E) a binder polymer as necessary. A layer is provided. The components in the photosensitive layer will be specifically described below.

<(A) Sensitizing dye>
As a sensitizing dye that can be a component of the photopolymerizable photosensitive layer composition of the present invention, a chemical change is caused by interaction with a spectral sensitizing dye and an electronically excited state caused by light absorption of the sensitizing dye, and a radical or Examples include dyes or pigments that interact with an activator compound that generates an acid.
Preferred spectral sensitizing dyes or dyes include polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, thianes). Carbocyanine, oxacarbocyanine), merocyanines (eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), phthalocyanines ( For example, phthalocyanine, metal phthalocyanine), porphyrins (for example, tetraphenylporphyrin, central metal-substituted porphyrin), chlorophylls (for example, chlorophyll, chlorophyllin, central gold) Substituted chlorophyll), metal complexes (for example, the following structure),

Anthraquinones (for example, anthraquinone), squariums (for example, squalium) and the like can be mentioned.
Examples of more preferable spectral sensitizing dyes or dyes include styryl dyes described in JP-B-37-13034, for example,

Cationic dyes described in JP-A-62-143044, for example,

Quinoxalinium salts described in JP-B-59-24147, for example,

New methylene blue compounds described in JP-A-64-33104, for example,

Anthraquinones described in JP-A No. 64-56767, for example,

Benzoxanthene dyes described in JP-A-2-17714, acridines described in JP-A-2-226148 and JP-A-2-226149, for example,

The pyrylium salts described in Japanese Patent Publication No. 40-28499, for example,

Cyanines described in JP-B-46-42363, for example,

Benzofuran dyes described in JP-A-2-63053, for example,

Conjugated ketone dyes described in JP-A-2-85858 and JP-A-2-216154, for example,

A dye described in JP-A No. 57-10605, an azocinnamilidene derivative described in JP-B-2-30321, for example,

Cyanine dyes described in JP-A-1-287105, for example,

JP 62-31844, JP 62-31848, JP 62-1430
Xanthene dyes described in No. 43, for example,

Aminostyryl ketone described in JP-B-59-28325, for example,

Merocyanine dyes represented by the following general formulas [1] to [8] described in JP-B-61-9621,

(In the general formulas [3] to [8], X ⁸ represents a hydrogen atom, an alkyl group, a substituted alkyl group, an alkoxy group, an aryl group, a substituted aryl group, an aryloxy group, an aralkyl group or a halogen atom. In the general formulas [1] to [8], R ⁴⁸ , R ⁴⁹ and R ⁵⁰ are each an alkyl group, a substituted alkyl group, an alkenyl group, an aryl group, a substituted aryl group or an aralkyl group. And may be equal to or different from each other.), Dyes represented by the following general formulas [9] to [11] described in JP-A-2-17943,

(In the formula, A represents an oxygen atom, sulfur atom, selenium atom, tellurium atom, alkyl or aryl-substituted nitrogen atom or dialkyl-substituted carbon atom. Y ³ represents a hydrogen atom, alkyl group, substituted alkyl group, aryl. A group, a substituted aryl group, an aralkyl group, an acyl group, or a substituted alkoxycarbonyl group, wherein R ⁵¹ and R ⁵² each independently represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or a substituent, R ⁵³ O— ,

- represents a _{(CH 2 CH 2 O) w} -R 53, a halogen atom (F, Cl, Br, I ) substituted alkyl group having 1 to 18 carbon atoms having a. R ⁵³ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and B represents a dialkylamino group, a hydroxyl group, an acyloxy group, a halogen atom, or a nitro group. w represents an integer of 0 to 4, and x represents an integer of 1 to 20. ), A merocyanine dye represented by the following general formula [12] described in JP-A-2-244050,

(Wherein R ⁵⁴ and R ⁵⁵ each independently represents a hydrogen atom, an alkyl group, a substituted alkyl group, an alkoxycarbonyl group, an aryl group, a substituted aryl group or an aralkyl group. A ² represents an oxygen atom, a sulfur atom or a selenium atom. Represents a tellurium atom, an alkyl or aryl-substituted nitrogen atom, or a dialkyl-substituted carbon atom, X ⁹ represents a group of non-metallic atoms necessary to form a nitrogen-containing hetero five-membered ring, and Y ⁴ represents a substituted Z ³ represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, an alkoxy group, a phenyl group, an unsubstituted or substituted polynuclear aromatic ring, or an unsubstituted or substituted heteroaromatic ring. group, an alkylthio group, an arylthio group, a substituted amino group, an acyl group or an alkoxycarbonyl group, together with Y ⁴ And may be bonded to form a ring). As a preferable specific example, for example,

A merocyanine dye represented by the following general formula [13] described in JP-B-59-28326,

(In the formula, R ⁵⁶ and R ⁵⁷ each represent a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group or an aralkyl group, which may be the same or different from each other. X ¹⁰ represents Hammett ( Hammett) represents a substituent having a sigma (σ) value in the range of −0.9 to +0.5), and is represented by the following general formula [14] described in JP-A-59-89303. Merocyanine dye,

(Wherein R ⁵⁸ and R ⁵⁹ each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group or an aralkyl group. X ¹¹ is a Hammett sigma (σ) value) .Y ⁵ representing a substituent in the range from -0.9 to +0.5 represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, an acyl group or an alkoxycarbonyl group. ), As a preferred specific example, for example,

A merocyanine dye represented by the following general formula [15] described in JP-A-8-129257;

(Wherein R ⁶⁰ , R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁸ , R ⁶⁹ , R ⁷⁰ , R ⁷¹ are each independently a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted group) Aryl, hydroxyl, substituted oxy, mercapto, substituted thio, amino, substituted amino, substituted carbonyl, sulfo, sulfonate, substituted sulfinyl, substituted sulfonyl, phosphono, substituted phosphono, phosphonate A group, a substituted phosphonate group, a cyano group, a nitro group, or R ⁶⁰ and R ⁶¹ , R ⁶¹ and R ⁶² , R ⁶² and R ⁶³ , R ⁶⁸ and R ⁶⁹ , R ⁶⁹ and R ⁷⁰ , R ⁷⁰ R ⁷¹ may be bonded to each other to form an aliphatic or aromatic ring, R ⁶⁴ represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group, R ⁶⁵ represents a substituted,
Or an unsubstituted alkenylalkyl group or a substituted or unsubstituted alkynylalkyl group, wherein R ⁶⁶ and R ⁶⁷ are each independently a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group. Represents a substituted carbonyl group. ), As a preferred specific example, for example,

  More preferable specific examples include compounds represented by the following general formulas (XIV) to (XVIII).

(In the formula (XIV), A ¹ represents a sulfur atom or NR ⁵⁰ , R ⁵⁰ represents an alkyl group or an aryl group, and L ² represents a basic nucleus of the dye in combination with the adjacent A ² and the adjacent carbon atom. Represents a nonmetallic atomic group to be formed, R ⁵¹ and R ⁵² each independently represent a hydrogen atom or a monovalent nonmetallic atomic group, and R ⁵¹ and R ⁵² are bonded to each other to form an acidic nucleus of the dye. W represents an oxygen atom or a sulfur atom.)

  Preferred specific examples of the compound represented by the general formula (XIV) are shown below.

(In Formula (XV), Ar ¹ and Ar ² each independently represent an aryl group, and are linked via a bond with —L ³ —, where L ³ represents —O— or —S—. W is synonymous with that shown in the general formula (XIV).)

  Preferable examples of the compound represented by the general formula (XV) include the following.

(In the formula (XVI), A ² represents a sulfur atom or NR ⁵⁹ , L ⁴ represents a nonmetallic atomic group that forms a basic nucleus of the dye together with adjacent A ² and a carbon atom, R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ and R ⁵⁸ each independently represent a monovalent nonmetallic atomic group, and R ⁵⁹ represents an alkyl group or an aryl group.)

  Preferable examples of the compound represented by the general formula (XVI) include the following.

(In Formula (XVII), A ³ and A ⁴ each independently represent —S— or —NR ⁶² — or —NR ⁶³ —, and R ⁶³ and R ⁶⁴ each independently represents a substituted or unsubstituted alkyl group, substituted Alternatively, it represents an unsubstituted aryl group, and L ⁵ and L ⁶ each independently represents a nonmetallic atomic group that forms a basic nucleus of a dye in combination with adjacent A ³ , A ⁴ and adjacent carbon atoms. , R ⁶⁰ and R ⁶¹ are each independently a monovalent non-metallic atomic group or can be bonded to each other to form an aliphatic or aromatic ring.)

  Preferable examples of the compound represented by the general formula (XVII) include the following.

(In the formula (XVIII), R ⁶⁶ represents an aromatic ring or a hetero ring which may have a substituent, and A ⁵ represents an oxygen atom, a sulfur atom or —NR ⁶⁷ —. R ⁶⁴ , R ⁶⁵ and R ⁶⁷ each independently represents a hydrogen atom or a monovalent non-metallic atomic group, and R ⁶⁷ and R ⁶⁴ , and R ⁶⁵ and R ⁶⁷ may be bonded to each other to form an aliphatic or aromatic ring. it can.)

  Preferable specific examples of the compound represented by the general formula (XVIII) include those shown below.

A benzopyran dye represented by the following general formula [16] described in JP-A-8-334897, for example,

(Wherein R ^{72 to} R ⁷⁵ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a hydroxyl group, an alkoxy group or an amino group. R ^{72 to} R ⁷⁵ are carbons to which they can be bonded respectively. A ring composed of a non-metal atom may be formed together with an atom, R ⁷⁶ represents a hydrogen atom, an alkyl group, an aryl group, a heteroaromatic group, a cyano group, an alkoxy group, a carboxy group or an alkenyl group, and R ⁷⁷ represents A group represented by R ⁷⁶ or —Z—R ⁷⁶ , wherein Z represents a carbonyl group, a sulfonyl group, a sulfinyl group or an arylene carbonyl group, and R ⁷⁶ and R ⁷⁷ together form a ring composed of a nonmetallic atom; A represents an O atom, S atom, NH or an N atom having a substituent, B represents an O atom, or a group of = C (G1) (G2), G1 and G2 may be the same or different. May be A hydrogen atom, a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, an arylcarbonyl group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, or a fluorosulfonyl group, provided that G1 and G2 are the same. G1 and G2 may form a ring composed of a nonmetallic atom together with a carbon atom), and the like.

In addition, the following infrared absorbers (dyes or pigments) are particularly preferably used as the sensitizing dye.
Examples of preferable dyes include cyanine dyes described in JP-A-58-125246, JP-A-59-84356, JP-A-59-202829, JP-A-60-78787, and the like. Examples include cyanine dyes described in Japanese Patent No. 434,875.

  Further, near infrared absorption sensitizers described in US Pat. No. 5,156,938 are also preferably used, and further substituted aryl benzoates described in US Pat. No. 3,881,924 are also used. (Thio) pyrylium salt, trimethine thiapyrylium salt described in JP-A-57-142645 (US Pat. No. 4,327,169), JP-A-58-181051, JP-A-58-2220143, 59-41363, 59-84248, 59-84249, 59-146063, 59-146061, pyrylium compounds described in JP-A-59-216146, and cyanine described in JP-A-59-216146 Dyes, pentamethine thiopyrylium salts described in US Pat. No. 4,283,475, etc., and Japanese Patent Publication Nos. 5-13514 and 5-19702. Pyrylium compounds as mounting is also preferably used.

  Also preferred are near-infrared absorbing dyes described as formulas (I) and (II) in US Pat. No. 4,756,993 and phthalocyanine dyes described in EP 916513. Can be mentioned.

  Furthermore, the anionic infrared absorber illustrated below can also be used conveniently. An anionic infrared absorbing agent refers to an anionic infrared absorbing agent having an anionic structure without a cationic structure in the mother nucleus of a dye that substantially absorbs infrared rays. Examples include (c1) anionic metal complexes, (c2) anionic carbon black, (c3) anionic phthalocyanine, and (c4) compounds represented by the following general formula (IX). The counter cation of these anionic infrared absorbers is a monovalent cation containing a proton or a polyvalent cation.

  Here, the (c1) anionic metal complex refers to a substance that becomes an anion in the central metal and the entire ligand of the complex part that substantially absorbs light.

  Examples of (c2) anionic carbon black include carbon black to which anionic groups such as sulfonic acid, carboxylic acid, and phosphonic acid groups are bonded as substituents. In order to introduce these groups into carbon black, as described in Carbon Black Handbook 3rd Edition (Edited by Carbon Black Association, April 5, 1995, published by Carbon Black Association), page 12, What is necessary is just to take means, such as oxidizing carbon black.

  (C3) Anionic phthalocyanine refers to a phthalocyanine skeleton bonded with the anionic group previously mentioned in the description of (c2) as a substituent to form an anion as a whole.

Next, the compound represented by (c4) general formula (IX) will be described in detail. In the general formula (IX), G _a ^- represents an anionic substituent, G _b represents a neutral substituent. X ^{m +} represents a 1 to m-valent cation containing a proton, and m represents an integer of 1 to 6. M represents a conjugated chain, and this conjugated chain M may have a substituent or a ring structure. The conjugated chain M can be represented by the following formula.

In the formula, R ¹ , R ² and R ³ are each independently a hydrogen atom, halogen atom, cyano group, alkyl group, aryl group, alkenyl group, alkynyl group, carbonyl group, thio group, sulfonyl group, sulfinyl group, oxy A group and an amino group, which may be linked to each other to form a ring structure. n represents an integer of 1 to 8.

  Of the anionic infrared absorbers represented by the general formula (IX), A-1 to A-5 shown below are preferably used.

  Moreover, the cationic infrared absorber shown as the following CA-1-CA-44 can also be used preferably.

In the structural formula, T ⁻ represents a monovalent counter anion, preferably a halogen anion (F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ ), a Lewis acid anion (BF ₄ ⁻ , PF ₆ ⁻ , SbCl _6). ⁻ , ClO ₄ ⁻ ), an alkyl sulfonate anion, and an aryl sulfonate anion.

  The alkyl of the alkyl sulfonic acid means a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, a butyl group. , Pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, s-butyl, t- A 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 can be exemplified. 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.

  The aryl of the aryl sulfonic acid includes one consisting of one benzene ring, one in which two or three benzene rings form a condensed ring, one in which a benzene ring and a five-membered unsaturated ring form a condensed ring, etc. 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, and among these, a phenyl group and a naphthyl group are more preferable.

  Moreover, the nonionic infrared absorber shown as NA-1 to NA-12 below can also be used preferably.

  Among the exemplified compounds, A-1 is particularly preferable as the anionic infrared absorber, and CA-7, CA-30, CA-40, and CA-42 are nonionic infrared absorption as the cationic infrared absorber. Examples of the agent include NA-11.

As other dyes, 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,
Examples thereof include metal complex azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, diimmonium dyes, aminium dyes, squarylium dyes, and metal thiolate complexes.

  Examples of pigments that can be used as sensitizing dyes include commercially available pigments and the Color Index (CI) manual, “Latest Pigment Handbook” (edited by the Japan Pigment Technology Association, published in 1977), “Latest Pigment Application Technology”. (CMC Publishing, published in 1986) and “Printing Ink Technology” published by CMC Publishing, published in 1984) can be used. For example, types of pigments 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 surface treatment methods are described in “Characteristics and Applications of Metal Soap” (Sachibo), “Printing Ink Technology” (CMC Publishing, 1984) and “Latest Pigment Application Technology” (CMC Publishing, 1986). Yes.

  The particle size of the pigment is preferably 0.01 μm to 10 μm, more preferably 0.05 μm to 1 μm, and particularly preferably 0.1 μm to 1 μm. If the particle diameter of the pigment is in the above range, the stability and uniformity of the dispersion in the photosensitive layer coating solution will be good.

  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).

Still more preferred examples of the sensitizing dye in the present invention include the merocyanine dye described in JP-B-61-9621, the merocyanine dye described in JP-A-2-17943, and the merocyanine described in JP-A-2-244050. Dyes, merocyanine dyes described in JP-B-59-28326, merocyanine dyes described in JP-A-59-89303, merocyanine dyes described in JP-A-8-129257, and benzopyrans described in JP-A-8-334897 Mention may be made of pigments. Furthermore, the infrared absorber of Unexamined-Japanese-Patent No. 11-209001 can also be mentioned.
The sensitizing dye in the present invention is suitably used alone or in combination of two or more.
Further, the photopolymerizable composition for forming the photosensitive layer of the present invention may contain a known compound having a function of further improving sensitivity or suppressing polymerization inhibition by oxygen as a co-sensitizer.

Examples of such co-sensitizers include amines such as MR Sander et al., “Journal of Polymer Society”, Vol. 10, page 3173 (1972), Japanese Patent Publication No. 44-20189, Japanese Patent Laid-Open No. 51-82102, JP 52-134692, JP 59-138205, JP 60-84305, JP 62-18537, JP 64-33104, Rese
Examples include compounds described in arch Disclosure 33825, and specific examples include triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline, and the like.

  Other examples of co-sensitizers include thiols and sulfides such as thiol compounds described in JP-A-53-702, JP-B-55-500806, JP-A-5-142772, and JP-A-56- And the like, and specific examples include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercaptonaphthalene. Etc.

  Other examples include amino acid compounds (eg, N-phenylglycine), organometallic compounds described in Japanese Patent Publication No. 48-42965 (eg, tributyltin acetate), and hydrogen described in Japanese Patent Publication No. 55-34414. Examples include donors, sulfur compounds described in JP-A-6-308727 (eg, trithiane), phosphorus compounds described in JP-A-6-250389 (diethylphosphite, etc.), and the like.

Further, when a sensitizing dye is used in the present invention, an activator compound that generates a radical or an acid by causing a chemical change by interaction with an electronically excited state generated by light absorption of the sensitizing dye in the photopolymerizable composition; The molar ratio of the sensitizing dye is preferably 99: 1 to 1:99, more preferably 90:10 to 10:90, and most preferably 80:20 to 20:80.
When using the above-mentioned co-sensitizer, it is appropriate to use 0.01 to 50 parts by weight, more preferably 0.02 to 20 parts by weight, most preferably with respect to 1 part by weight of the photopolymerization initiator. Is 0.05 to 10 parts by mass.

<(B) An activator compound that undergoes a chemical change by interaction with an electronically excited state caused by light absorption of a sensitizing dye to generate a radical or an acid>
Next, an activator compound (hereinafter simply referred to as “an activator compound”) that undergoes a chemical change by interaction with an electronically excited state generated by light absorption of a sensitizing dye contained in the photosensitive layer of the lithographic printing plate of the present invention to generate a radical or an acid. The abbreviated “activator compound” may be described.

The activator compound used in the present invention is not particularly limited, but a compound containing 4 or more aromatic rings in the molecule is preferable.
Preferred compounds containing four or more aromatic rings in the molecule include (a) aromatic ketones, (b) aromatic onium salt compounds, (c) organic peroxides, (d) hexaarylbiphenyls. Examples include imidazole compounds, (e) borate compounds, (f) metallocene compounds, and (g) compounds having a carbon halogen bond.

(A) As a preferable example of aromatic ketones, “RADIATION CURING IN POLYMER SCIENCE
AND TECHNOLOGY "JPFOUASSIER JFRABEK (1993), p77-117 compound having a benzophenone skeleton or thioxanthone skeleton, for example,

Etc. More preferable examples of (a) aromatic ketones include JP-B-47-641.
Α-thiobenzophenone compounds described in JP-A-6, benzoin ether compounds described in JP-B-47-3981, benzoin derivatives described in JP-B-47-23664, aroylphosphonic acid described in JP-A-57-30704 Esters, dialkoxybenzophenones described in JP-B-60-26483, for example, the following structures are exemplified.

  Another example of the activator compound (b) as an aromatic onium salt is an element of groups V, VI and VII of the periodic table, specifically N, P, As, Sb, Bi, O , S, Se, Te, or I aromatic onium salts. Examples of such aromatic onium salts include compounds shown in JP-B 52-14277, JP-B 52-14278, and JP-B 52-14279. Specifically, the following structures can be mentioned.

  (C) “Organic peroxide” as another example of the activator compound used in the present invention includes almost all organic compounds having one or more oxygen-oxygen bonds in the molecule. Examples include 3,3'4,4'-tetra- (cumylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone, and the like.

Other examples of the activator compound used in the present invention include (d) hexaarylbiimidazoles such as the lophine dimers described in JP-B Nos. 45-37377 and 44-86516, such as 2,2 '-Bis (o-chlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-bromophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole Imidazole, 2,2'-bis (o, p-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5 5'-tetra (m-methoxyphenyl) biimidazole, 2,2'-bis (o, o'-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis ( o- Trophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-methylphenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2 Examples include '-bis (o-trifluorophenyl) -4,4', 5,5'-tetraphenylbiimidazole.

  As an example of the (e) borate salt which is another example of the activator compound in the present invention, a compound represented by the following general formula [I] can be mentioned.

(Wherein R ²² , R ²³ , R ²⁴ and R ²⁵ may be the same or different from each other, and each represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, A substituted or unsubstituted alkynyl group or a substituted or unsubstituted heterocyclic group, R ²² , R ²³ , R ²⁴ and R ²⁵ may be combined with each other to form a cyclic structure; Provided that at least one of R ²² , R ²³ , R ²⁴ and R ²⁵ is a substituted or unsubstituted alkyl group, and Z ⁺ represents an alkali metal cation or a quaternary ammonium cation).
Examples of the alkyl group for R ^{22 to} R ²⁵ include linear, branched, and cyclic groups, and those having 1 to 18 carbon atoms are preferable. Specifically, methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, octyl, stearyl, cyclobutyl, cyclopentyl, cyclohexyl and the like are included. Examples of the substituted alkyl group include the above alkyl groups, halogen atoms (for example, —Cl, —Br, etc.), cyano groups, nitro groups, aryl groups (preferably phenyl groups), hydroxy groups,

(Wherein R ²⁶ and R ^{27 each} independently represents a hydrogen atom, an alkyl group having 1 to 14 carbon atoms, or an aryl group), —COOR ²⁸ (where R ²⁸ is a hydrogen atom, having 1 to 14 carbon atoms) An alkyl group or an aryl group), -OCOR ²⁹ or -OR ³⁰ (wherein R ²⁹ and R ³⁰ represent an alkyl group having 1 to 14 carbon atoms or an aryl group) as a substituent. included.
The aryl groups of R ^{22 to} R ²⁵ include 1 to 3 ring aryl groups such as a phenyl group and a naphthyl group, and the substituted aryl group is a substitution of the above substituted alkyl group with the above aryl group. Those having a group or an alkyl group having 1 to 14 carbon atoms are included.
Examples of the alkenyl group of R ^{22 to} R ²⁵ include linear, branched, and cyclic groups having 2 to 18 carbon atoms, and examples of the substituent of the substituted alkenyl group include the substituents of the substituted alkyl group. Is included.
Examples of the alkynyl group of R ^{22 to} R ²⁵ include linear or branched groups having 2 to 28 carbon atoms, and examples of the substituent of the substituted alkynyl group include those listed as the substituents of the substituted alkyl group. included.
In addition, examples of the heterocyclic group of R ^{22 to} R ²⁵ include a 5-membered or more, preferably 5 to 7-membered heterocyclic group containing at least one of N, S, and O. May contain a condensed ring. Furthermore, you may have what was mentioned as a substituent of the above-mentioned substituted aryl group as a substituent.
Specific examples of the compound represented by the general formula [I] are described in US Pat. Nos. 3,567,453, 4,343,891, European Patents 109,772, and 109,773. And the compounds shown below.

  Examples of (f) metallocene compounds which are other examples of activator compounds include JP-A 59-152396, JP-A 61-151197, JP-A 63-41484, JP-A 2-249, Examples thereof include titanocene compounds described in JP-A-2-4705 and iron-arene complexes described in JP-A-1-304453 and JP-A-1-152109.

Specific examples of the titanocene compound include di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl. Di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4,6-trifluorophen-1 -Yl, di-cyclopentadienyl-Ti-2,6-difluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4-difluorophen-1-yl, di-methylcyclopenta Dienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1 − Di-methylcyclopentadienyl-Ti-bis-2,4-difluorophen-1-yl, bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyridin-1-yl) Phenyl) titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (methylsulfonamido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- Butylbialoyl-amino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-ethylacetylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-methylacetyl) Amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-ethylpropionylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3 -(N-ethyl- (2,2-dimethylbutanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-butyl- (2,2-dimethylbutane) Noyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-pentyl- (2,2-dimethylbutyl) Noyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-hexyl)-(2,2-dimethylbutanoyl) phenyl] titanium, bis (cyclopentadienyl) ) Bis [2,6-difluoro-3- (N-methylbutyrylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-methylpentanoylamino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-ethylcyclohexylcarbonylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-ethyl) Isobutyrylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-ethylacetylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6- Difluoro-3- (2,2,5,5-tetramethyl-1,2,5-azadisilolidin-1-yl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- ( Octylsulfonamido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (4-tolylsulfonamide) Phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (4-dodecylphenyl sulfonyl) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3- (4- (1-pentylheptyl) phenylsulfonylamido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3 -(Ethylsulfonylamido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3-((4-bromophenyl) -sulfonylamido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2-naphthylsulfonylamido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (hexadecylsulfonylamido) phenyl] titanium, bis (cyclo Pentadienyl) bis [2,6-difluoro-3- (N-methyl- (4-dodecylphenyl)] Ruhoniruamido) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-methyl-4- (1-pentylheptyl) phenyl) sulfonylamide)] titanium, bis (cyclopentadienyl) bis [2,6 -Difluoro-3- (N-hexyl- (4-tolyl) -sulfonylamido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (pyrrolidine-2,5-dioni-1) -Yl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (3,4-dimethyl-3-pyrrolidin-2,5-dioni-1-yl) phenyl] titanium, bis (Cyclopentadienyl) bis [2,6-difluoro-3- (phthalimido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3 Isobutoxycarbonylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (ethoxycarbonylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro- 3-((2-chloroethoxy) -carbonylamino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3- (phenoxycarbonylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (3-phenylthioureido) Phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (3-butylthioureido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- ( 3-phenylureido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (3-butylureido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro -3- (N, N-diacetylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro 3- (3,3-dimethyl-ureido) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3- (acetylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (butyrylamino) phenyl] titanium, bis (Cyclopentadienyl) bis [2,6-difluoro-3- (decanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (octadecanoylamino) phenyl] Titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (isobutyrylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2-ethyl) Hexanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2-methylbuta) Ylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (pivaloylamino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3- (2,2-dimethylbutanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2 -Ethyl-2-methylheptanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (cyclohexylcarbonylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2 , 6-Difluoro-3- (2,2-dimethyl-3-chloropropanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (3-phenylpropanoylamino) Phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2-chloromethyl-2-methyl) 3-chloro-propanoylamino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3- (3,4-xyloylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (4- Ethylbenzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2,4,6-mesitylcarbonylamino) phenyl] titanium, bis (cyclopentadienyl) bis [ 2,6-difluoro-3- (benzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3-phenylpropyl) benzoylamino) phenyl] titanium, bis (Cyclopentadienyl) bis [2,6-difluoro-3- (N- (3-ethylheptyl) -2,2-dimethylpentanoylamino ] Phenyl titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-isobutyl- (4-toluyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6- Difluoro-3- (N-isobutylbenzoylamino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-cyclohexylmethylpivaloylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N -(Oxolan-2-ylmethyl) benzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3-ethylheptyl) -2,2-dimethylbutanoylamino ) Phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3-phenylpropyl- (4-toluyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (oxolani-2-ylmethyl)-(4-toluyl) amino) phenyl] titanium, bis (si Ropentajieniru) bis [2,6-difluoro -3- (N- (4- Toruirumechiru) benzoylamino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (4-toluylmethyl)-(4-toluyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 -Difluoro-3- (N-butylbenzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-butyl- (4-toluyl) amino) phenyl] titanium, bis (Cyclopentadienyl) bis [2,6-difluoro-3- (N-hexyl- (4-toluyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- ( N- (2,4-dimethylpentyl) -2,2-dimethylbutanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro- - (2,4-dimethylpentyl) -2,2-dimethyl pentanoylamino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3-((4-toluyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2,2 -Dimethylpentanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2,2-dimethyl-3-ethoxypropanoylamino) phenyl] titanium, bis (cyclopentadi) Enyl) bis [2,6-difluoro-3- (2,2-dimethyl-3-allyloxypropanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N -Allylacetylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2-ethylbutanoylamino) Phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3-(N-cyclohexylmethyl-benzoylamino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-cyclohexylmethyl- (4-toluyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3 -(N- (2-ethylhexyl) benzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-isopropylbenzoylamino) phenyl] titanium, bis (cyclopentadienyl) ) Bis [2,6-difluoro-3- (N- (3-phenylpropyl) -2,2-dimethylpentanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro- 3- (N-hexylbenzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro -3-(N-cyclohexylmethyl-2,2-dimethyl-pentanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [
2,6-difluoro-3- (N-butylbenzoylamino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (2-ethylhexyl) -2,2-dimethylpentanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2 , 6-Difluoro-3- (N-hexyl-2,2-dimethylpentanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-isopropyl-2,2 -Dimethylpentanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3-phenylpropyl) pivaloylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-butyl-2,2-dimethylpentanoylamino) phenyl] titanium, bis (cyclo Ntajieniru) bis [2,6-difluoro -3- (N- (2- methoxyethyl) benzoylamino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-benzylbenzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-benzyl- (4-Toluyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (2-methoxyethyl)-(4-toluyl) amino) phenyl] titanium, bis (Cyclopentadienyl) bis [2,6-difluoro-3- (N- (4-methylphenylmethyl) -2,2-dimethylpentanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2 , 6-Difluoro-3- (N- (2-methoxyethyl) -2,2-dimethylpentanoylamino) phenyl] titanium, bis (cyclopentadiene) Le) bis [2,6-difluoro-3-(N-cyclohexylmethyl - (2-ethyl-2-methyl-heptanoyl) amino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-butyl- (4-chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3 -(N-hexyl- (2-ethyl-2-methylbutanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-cyclohexyl-2,2-dimethyl) Pentanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (oxolani-2-ylmethyl) -2,2-dimethylpentanoyl) amino) phenyl] titanium Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-cyclohexyl- (4-chlorobenzoyl) amino) phenyl Titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-cyclohexyl- (2-chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro -3- (3,3-dimethyl-2-azetidinoni-1-yl) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3-isocyanatophenyl) titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-ethyl- (4-tolylsulfonyl) ) Amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-hexyl- (4-tolylsulfonyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [ 2,6-difluoro-3- (N-butyl- (4-tolylsulfonyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-isobutyl- (4- Tolylsulfonyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-butyl- (2,2-di) Chill -3 chloropropanoyl) amino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3-phenylpropanoyl) -2,2-dimethyl-3-chloropropanoyl) amino) phenyl] titanium, bis (cyclopenta Dienyl) bis [2,6-difluoro-3- (N-cyclohexylmethyl- (2,2-dimethyl-3-chloropropanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 -Difluoro-3- (N-isobutyl- (2,2-dimethyl-3-chloropropanoyl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-butyl- ( 2-chloromethyl-2-methyl-3-chloropropanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3 (Butyl thiocarbonyl amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (phenylthio carbonylamino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3-isocyanatophenyl) titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-ethyl- (4-tolylsulfonyl) ) Amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-hexyl- (4-tolylsulfonyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [ 2,6-difluoro-3- (N-butyl- (4-tolylsulfonyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-isobutyl- (4- Tolylsulfonyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-butyl- (2,2-di) Til-3-chloropropanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3-phenylpropanoyl) -2,2-dimethyl-3- Chloropropanoyl) amino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-cyclohexylmethyl- (2,2-dimethyl-3-chloropropanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-isobutyl- (2,2-dimethyl-3-chloropropanoyl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N -Butyl- (2-chloromethyl-2-methyl-3-chloropropanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (butylthiocarbonylamino) phenyl] Titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (phenylthiocarbonylamino) phenyl] titanium, bis Methylcyclopentadienyl) bis [2,6-difluoro-3-(N-hexyl-2,2-dimethyl-butanoylamino) amino) phenyl] titanium,

Bis (methylcyclopentadienyl) bis [2,6-difluoro-3- (N-hexyl-2,2-dimethylpentanoylamino) phenyl] titanium, bis (methylcyclopentadienyl) bis [2,6- Difluoro-3- (N-ethylacetylamino) phenyl] titanium, bis (methylcyclopentadienyl) bis [2,6-difluoro-3- (N-ethylpropionylamino) phenyl] titanium, bis (trimethylsilylpentadienyl) ) Bis [2,6-difluoro-3- (N-butyl-2,2-dimethylpropanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- ( 2-methoxyethyl) -trimethylsilylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6- Fluoro-3- (N-butylhexyldimethylsilylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-ethyl- (1,1,2, -trimethylpropyl) Dimethylsilylamino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3- (3-ethoxymethyl-3-methyl-2-azethiodinon-1-yl) phenyl] titanium, bis (cyclopentadienyl) bis [2, 6-difluoro-3- (3-allyloxymethyl-3-methyl-2-azetidinon-1-yl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (3-chloro Methyl-3-methyl-2-azetidinoni-1-yl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-benzyl-2,2-dimethylpropanoylamino) phenyl ] Titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (5,5-dimethyl-2-pyrrolidinoni-1-yl) phenyl] tita , Bis (cyclopentadienyl) bis [2,6-difluoro-3- (6,6-diphenyl-2-Piperijinoni-1-yl) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (2,3-dihydro-1,2-benzisothiazolo-3-one (1,1-dioxide) -2-yl) phenyl] Titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-hexyl- (4-chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro -3- (N-hexyl- (2-chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-isopropyl- (4-chlorobenzoyl) amino) Phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (4-methylphenylmethyl)-(4-chlorobenzoyl) a Roh) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3-(N-(4-methylphenyl methyl) - (2-chlorobenzoyl) amino) phenyl] titanium,

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

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

  Furthermore, other preferred examples of the active compound (g) are compounds represented by the following general formulas [II] to [V], and the following general formula [VI]. A carbonylmethylene heterocyclic compound having a trihalogenomethyl group, a 4-halogeno-5- (halogenomethyl-phenyl) -oxazole derivative represented by the following general formula [VII], and a general formula [VIII] 2- (halogenomethyl-phenyl) -4-halogeno-oxazole derivatives.

(In the formula, X ² represents a halogen atom. Y ² represents —C (X ² ) ₃ , —NH ₂ , —NHR ³² , —NR ³² , —OR ³² , where R ³² represents an alkyl group or a substituted group. An alkyl group, an aryl group, or a substituted aryl group, and R ³¹ represents —C (X ² ) ₃ , an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or a substituted alkenyl group.

(Wherein R ³³ is an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group, a substituted aryl group, a halogen atom, an alkoxy group, a substituted alkoxyl group, a nitro group or a cyano group, and X ³ is A halogen atom, and n is an integer of 1 to 3.)

(Wherein R ³⁴ is an aryl group or a substituted aryl group, and R ³⁵ is

Or Z ² is —C (═O) —, —C (═S) — or —SO ₂ —, and R ³⁶ and R ³⁷ are alkyl groups, substituted alkyl groups, alkenyl groups, substituted alkenyl groups. , An aryl group or a substituted aryl group, R ³⁸ is the same as R ³² in the general formula [IV], X ³ is a halogen atom, and m is 1 or 2. )

Wherein R ³⁹ is an optionally substituted aryl group or heterocyclic group, R ⁴⁰ is a trihaloalkyl group or trihaloalkenyl group having 1 to 3 carbon atoms, and p is 1, 2 or 3)

Wherein L is a hydrogen atom or a substituent of the formula: CO— (R ⁴¹ ) _q (C (X ⁴ ) ₃ ) _r , Q is a sulfur, selenium or oxygen atom, dialkylmethylene group, alkene-1, 2-Irene group, 1,2-phenylene group or N—R group, M is a substituted or unsubstituted alkylene group or alkenylene group, or 1,2-arylene group, R ⁴² is an alkyl group , An aralkyl group or an alkoxyalkyl group, R ⁴¹ is a carbocyclic or heterocyclic divalent aromatic group, X ⁴ is a chlorine, bromine or iodine atom, and q = 0 and r = 1 Or q = 1 and r = 1 or 2.)

(In the formula, X ⁵ is a halogen atom, t is an integer of 1 to 3, s is an integer of 1 to 4, R ⁴³ is a hydrogen atom or a CH _3−t X ⁵ _t group, R ⁴⁴ is an s-valent unsaturated organic group which may be substituted.

(Wherein X ⁶ is a halogen atom, v is an integer of 1 to 3, u is an integer of 1 to 4, R ⁴⁵ is a hydrogen atom or a CH _3-v X6 _v group, R ⁴⁶ Is an unsaturated organic group which may be substituted.

  Specific examples of such a compound having a carbon-halogen bond include, for example, compounds described in German Patent No. 3333724, for example,

Etc.
Further, compounds described in JP-A-62-258241, for example,

Etc.

  Alternatively, those skilled in the art can easily follow the synthesis methods described in MP Hutt, EF Elslager and LM Herbel, “Journal of Heterocyclic chemistry”, Volume 7 (No. 3), pages 511 et seq. (1970). The following compound groups that can be synthesized:

Alternatively, the following compound group described in German Patent No. 3021590,

Can be mentioned.
Still more preferred examples of activator compounds in the present invention include (b) aromatic onium salts, (c) organic peroxides, (d) hexaarylbiimidazoles, (f) metallocene compounds, and (g) carbon. The compound which has a halogen bond can be mentioned, As a most preferable example, the titanocene compound in (f) and the compound which has (g) carbon halogen bond can be mentioned.
The activator compounds in the present invention are preferably used alone or in combination of two or more.

  The usage-amount of the activator compound in the composition in this invention is 0.01-60 mass% with respect to the mass of all the components of a photopolymerizable composition, More preferably, it is 0.05-30 mass%.

<(C) Addition-polymerizable compound that reacts with at least one of radical and acid>
The addition polymerizable compound that reacts with at least one of a radical and an acid used in the present invention (hereinafter sometimes simply referred to as “addition polymerizable compound”) has at least one terminal ethylenically unsaturated bond. , Preferably selected from compounds having two or more. Examples of the monomer include an ester of an unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and an aliphatic polyhydric alcohol compound, and the unsaturated carboxylic acid and fatty acid. And amides with an aromatic polyvalent amine compound.

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 di Acrylate, Tetraethylene glycol diacrylate, Pentaerythritol diacrylate, Pentaerythritol triacrylate , Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer.

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

  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.
Furthermore, the mixture of the above-mentioned ester monomer can also be mentioned.
Specific examples of an amide monomer of an aliphatic polyvalent amine compound and an unsaturated carboxylic acid include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexa. Examples include methylene bis-methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, and xylylene bismethacrylamide.

  Other examples include vinyls containing a hydroxyl group represented by the following general formula (X) in a polyisocyanate compound having two or more isocyanate groups per molecule described in JP-B-48-41708. Examples thereof include a vinylurethane compound containing two or more polymerizable vinyl groups in one molecule to which a monomer is added.

_{CH 2 = C (R) COOCH} 2 CH (R ') OH (X)
(However, R and R ′ represent H or CH _3. )

  Also, urethane acrylates as described in JP-A-51-37193, JP-A-48-64183, JP-B-49-43191, JP-B-52-30490 Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates obtained by reacting an epoxy resin with (meth) acrylic acid can be used. Furthermore, Journal of Japan Adhesion Association vol.20, No. 7, pages 300 to 308 (1984) as photocurable monomers and oligomers can also be used. In the present invention, these monomers can be used in a chemical form such as a prepolymer, that is, a dimer, a trimer and an oligomer, or a mixture thereof and a copolymer thereof.

  Moreover, 5-50 mass% (it abbreviates as% below) with respect to all the components of a photopolymerizable composition is preferable, and, as for these usage-amounts, More preferably, it is 10-40%. When the amount used is in the above range, good coating film formability and curability are obtained.

<(D) Plasticizer>
As the plasticizer which is an essential component of the photopolymerizable photosensitive layer of the lithographic printing plate of the present invention, known plasticizer compounds can be widely used. Examples of preferred plasticizers include phthalate compounds such as dioctyl phthalate, didodecyl phthalate, dimethyl glycol phthalate, adipate compounds such as dioctyl adipate, sebacate compounds such as dibutyl sebacate, triacetyl glycerin, triethylene Examples thereof include ester compounds such as glycol dicaprylate and phosphorus-containing compounds such as tricresyl phosphate. More preferred examples include compounds having at least 4 or more ester groups in the molecule, and among them, compounds having a molecular weight of 300 to 1000 are more preferred.
Although the example of a more preferable plasticizer is shown below, this invention is not limited to these.

The mechanism of the effect of improving the storage stability by adding these plasticizers is not clear, but by increasing the flexibility of the photopolymerizable photosensitive layer, curing of the film due to dark polymerization during storage, manifestation of inhibition, etc. is suppressed. As a result, it is presumed that a decrease in sensitivity due to a decrease in polymerization reactivity is suppressed.
These plasticizers can be mixed in an arbitrary amount in the entire photosensitive layer composition. A preferable addition amount is 50% by mass or less, more preferably 25% by mass or less, based on the mass of the addition polymerizable compound of component (B).

<(E) Binder polymer>
The photopolymerizable photosensitive layer of the lithographic printing plate of the present invention preferably contains a binder polymer in addition to the components (A) to (D). As such a binder polymer, as long as it is a linear organic polymer having compatibility with a photopolymerizable ethylenically unsaturated compound,
Any one can be used. Preferably, a linear organic high molecular weight polymer that is soluble in water or weakly alkaline water or swellable that enables water development or weak alkaline water development is selected. The binder polymer is appropriately selected and used depending on whether water, weak alkaline water or an organic solvent is used as a developer as well as a film forming agent of the composition. For example, when a water-soluble organic polymer is used, water development is possible. Examples of such a binder 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-B-54-25957, Those described in JP-A-54-92723, JP-A-59-53836, JP-A-59-71048, ie, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer Examples thereof include a polymer, a crotonic acid copolymer, a maleic acid copolymer, and a partially esterified maleic acid copolymer. 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 these, [benzyl (meth) acrylate / (meth) acrylic acid / other addition-polymerizable vinyl monomers as required] copolymer and [allyl (meth) acrylate / (meth) acrylic acid / as required Other addition-polymerizable vinyl monomers] copolymers are preferred. In addition, polyvinylpyrrolidone, polyethylene oxide and the like are also useful as binder polymers as water-soluble linear organic polymers. In order to increase the strength of the cured film, alcohol-soluble polyamide, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin are also useful.

  These binder polymers can be mixed in an arbitrary amount in the entire photosensitive layer composition. However, when it exceeds 90% by mass with respect to the mass of all the components of the photosensitive layer composition, it does not give a preferable result in terms of the image strength to be formed. Preferably it is 30 to 85%. Further, (C) the addition polymerizable compound and (E) the binder polymer are preferably in the range of 1/9 to 7/3 by mass ratio. A more preferable range is 3/7 to 5/5.

<(F) Others>
[Polymerization inhibitor]
In the present invention, in addition to the above basic components, a small amount of a thermal polymerization inhibitor is added to prevent unnecessary thermal polymerization of the addition polymerizable compound during the production or storage of the photopolymerizable photosensitive layer composition. Is desirable. 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 whole composition. If necessary, higher fatty acid derivatives such as behenic acid and behenic acid amide may be added to prevent polymerization inhibition due to oxygen and unevenly distributed on the surface of the photosensitive layer during the drying process after coating. Good. The amount of the higher fatty acid derivative added is preferably from about 0.5% to about 10% by weight of the total composition.

[Colorants, etc.]
Further, a dye or pigment may be added for the purpose of coloring the photosensitive 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 type photosensitive layer. Therefore, it is particularly preferable to use a pigment as the colorant. Specific examples include pigments such as phthalocyanine pigments, azo pigments, carbon black and titanium oxide, and dyes such as ethyl violet, crystal violet, azo dyes, anthraquinone dyes, and cyanine dyes. The addition amount of the dye and the pigment is preferably about 0.5% by mass to about 5% by mass of the total composition.

[Other additives]
Furthermore, in order to improve the physical properties of the cured film, known additives such as inorganic fillers and other oil-sensitizing agents that can improve the ink inking property on the surface of the photosensitive layer may be added.
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 provide an additive and an intermediate layer for improving the adhesion between the photosensitive layer and the support, and improving the development removability of the unexposed photosensitive layer. For example, by adding or undercoating a compound having a relatively strong interaction with the substrate, such as a compound having a diazonium structure or a phosphone compound, adhesion can be improved and printing durability can be increased. By adding or undercoating a hydrophilic polymer such as acid or polysulfonic acid, the developability of the non-image area is improved, and the stain resistance can be improved.

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

[Support]
In order to obtain the lithographic printing plate of the present invention, the photosensitive layer is provided on an aluminum support. As an aluminum support body, a conventionally well-known aluminum support body used for a lithographic printing plate can be used without limitation. The aluminum support to be used is preferably a dimensionally stable plate-like material. If necessary, the surface of the aluminum support is appropriately known for the purpose of imparting hydrophilicity or improving strength. May be subjected to manual processing.

A suitable aluminum support is a pure aluminum plate or an alloy plate containing aluminum as a main component and containing a trace amount of foreign elements, and may also be a plastic film on which aluminum is laminated or 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 used in the present invention is about 0.1 mm to 0.6 mm, preferably 0.15 mm to 0.4 mm, particularly preferably 0.2 mm to 0.3 mm.

The aluminum support is preferably subjected to surface treatment such as roughening (graining) treatment, immersion treatment in an aqueous solution of sodium silicate, potassium fluoride zirconate, phosphate, or anodization treatment. .
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, known methods such as a ball polishing method, a brush polishing method, a blast polishing method, a buffing method, and a polishing method can be used. In addition, as an electrochemical surface roughening method, there is a method of performing alternating current or direct current in an electrolytic solution such as hydrochloric acid or nitric acid. Further, as disclosed in JP-A-54-63902, a method in which both are combined can also be used. Further, prior to roughening the aluminum plate, for example, a degreasing treatment with a surfactant, an organic solvent, an alkaline aqueous solution, or the like is performed in order to remove rolling oil on the surface, if desired.

  Furthermore, an aluminum plate that has been roughened and then immersed in an aqueous sodium silicate solution can be preferably used. For example, as described in Japanese Patent Publication No. 47-5125, an aluminum plate that has been anodized and then immersed in an aqueous solution of an alkali metal silicate is preferably used. The anodizing treatment is carried out in an electrolytic solution in which an inorganic acid such as phosphoric acid, chromic acid, sulfuric acid or boric acid, or an organic acid such as oxalic acid or sulfamic acid, or a salt solution thereof, or a combination of two or more thereof, is used. This is carried out by passing an electric current using the aluminum plate as an anode.

Silicate electrodeposition as described in US Pat. No. 3,658,662 is also effective.
Further, a support body provided with electrolytic grains as disclosed in JP-B-46-27481, JP-A-52-58602, JP-A-52-30503, and the above-described anodizing treatment and sodium silicate treatment. A surface treatment in combination with is also useful.
Further, those obtained by sequentially performing mechanical surface roughening, chemical etching, electrolytic graining, anodizing treatment and sodium silicate treatment as disclosed in JP-A-56-28893 are also suitable.

Furthermore, after performing these treatments, water-soluble resins such as polyvinylphosphonic acid, polymers and copolymers having sulfonic acid groups in the side chain, polyacrylic acid, water-soluble metal salts (for example, zinc borate) or Those having a primer such as a yellow dye or an amine salt are also suitable.
Further, a sol-gel treated substrate in which a functional group capable of causing an addition reaction by a radical as disclosed in JP-A-7-159983 is covalently used.

Other preferred examples include those in which a water-resistant hydrophilic layer is provided as a surface layer on an arbitrary support. Examples of such a surface layer include a layer composed of an inorganic pigment and a binder described in US Pat. No. 3,055,295 and JP-A-56-13168, and a hydrophilic swelling described in JP-A-9-80744. Examples thereof include sol-gel films made of titanium oxide, polyvinyl alcohol, and silicic acids described in JP-A-8-507727.
These hydrophilic treatments are performed to make the surface of the support hydrophilic, in order to prevent harmful reaction of the photopolymerizable composition provided thereon, and to improve the adhesion of the photosensitive layer. It is given for the purpose.

[Protective layer]
In the photopolymerizable lithographic printing plate of the present invention, since exposure is usually performed in the air, a protective layer can be further provided on the photosensitive layer. The protective layer prevents a low molecular weight compound such as a basic substance existing in the atmosphere that inhibits an image forming reaction caused by exposure in the photosensitive layer from being mixed into the photosensitive layer, and enables exposure in the air. Therefore, the properties desired for such a protective layer are low permeability of the low-molecular compound, and further, the transmission of light used for exposure is not substantially inhibited, the adhesiveness with the photosensitive layer is excellent, and It is desirable that it can be easily removed in the development process after exposure. Such a device relating to the protective layer has been conventionally devised, and is described in detail in US Pat. No. 3,458,311 and JP-A-55-49729. As a material that can be used for the protective layer, for example, a water-soluble polymer compound that is relatively excellent in crystallinity is preferably used. Specifically, polyvinyl alcohol, polyvinyl pyrrolidone, acidic celluloses, gelatin, gum arabic, Water-soluble polymers such as acrylic acid are known, but among these, the use of polyvinyl alcohol as a main component gives the best results in terms of basic properties such as oxygen barrier properties and development removability. The polyvinyl alcohol used for the protective layer may be partially substituted with an ester, an ether, and an acetal as long as it contains an unsubstituted vinyl alcohol unit for having necessary oxygen barrier properties and water solubility. Similarly, some of them may have other copolymer components. Specific examples of polyvinyl alcohol include those having a hydrolysis rate of 71 to 100 mol% and a molecular weight in the range of 300 to 2400 in terms of weight average molecular weight. 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.

  The components of the protective layer (selection of PVA, use of additives), coating amount, etc. are selected in consideration of fogging, adhesion, and scratch resistance in addition to low molecular substance blocking properties and development removability. In general, the higher the hydrolysis rate of the PVA used (the higher the content of unsubstituted vinyl alcohol units in the protective layer), the higher the film thickness, the lower the blocking of low molecular substances, which is advantageous in terms of sensitivity. . However, when the blocking property of the low molecular weight substance is extremely increased, there arises a problem that unnecessary polymerization reaction occurs during production and raw storage, and unnecessary fogging and image line thickening occur during image exposure. In addition, adhesion to the image area and scratch resistance are extremely important in handling the plate. That is, when a hydrophilic layer made of a water-soluble polymer is laminated on an oleophilic polymer layer, film peeling due to insufficient adhesion tends to occur. On the other hand, various proposals have been made to improve the adhesion between these two layers. For example, an acrylic emulsion or a water-insoluble vinyl pyrrolide-vinyl acetate copolymer in a hydrophilic polymer mainly composed of polyvinyl alcohol. Examples are known in which sufficient adhesion is obtained by mixing 20 to 60% by mass and laminating on a polymerization layer. Any of these known techniques can be applied to the protective layer in the present invention. Such a protective layer coating method is described in detail in, for example, US Pat. No. 3,458,311 and JP-A-55-49729.

Furthermore, other functions can be imparted to the protective layer. For example, when laser light is used as the light source, the photosensitive composition is excellent in photosensitivity at the wavelength of the light source, but may not be sensitized at other wavelengths. For example, if the light source is in the infrared region of 750 nm or more, it can be used in a substantially bright room, but in fact, it may be sensitive to short-wave light such as light from a fluorescent lamp. In that case, it is preferable to add a colorant (such as a water-soluble dye) that is excellent in light transmittance of the light source and can efficiently absorb light having a wavelength of less than 700 nm.
As another example, if the light source is in the ultraviolet region of 450 nm or less, it can be used under a safelight substantially. However, in actuality, there are cases where exposure is made with visible light of 500 nm or more. In that case, the addition of a colorant (such as a water-soluble dye) that excels in light transmittance of the light source and can efficiently absorb light of 500 nm or more can further enhance the suitability for safelight without causing a decrease in sensitivity. be able to.

The photopolymerizable lithographic printing plate of the present invention is usually subjected to image exposure, and then an unexposed portion of the photosensitive layer is removed with a developer to obtain an image. Preferred developers for use in making a planographic printing plate from these photopolymerizable lithographic printing plates include those described in Japanese Examined Patent Publication No. 57-7427. Potassium acid, sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, tribasic ammonium phosphate, dibasic ammonium phosphate, sodium metasilicate, sodium bicarbonate, aqueous ammonia, etc. An aqueous solution of an inorganic alkali agent such as, or an organic alkali agent such as monoethanolamine or diethanolamine is suitable. It is added so that the concentration of such an alkaline solution is 0.1 to 10% by mass, preferably 0.5 to 5% by mass.
As a more preferred developer, a developer containing a nonionic compound described in JP-A No. 2002-202616, having a pH of 11.5 to 12.8, and an electric conductivity of 3 to 30 mS / cm is used. Can be mentioned.

Such an alkaline aqueous solution may contain a small amount of a surfactant, an organic solvent such as benzyl alcohol, 2-phenoxyethanol, and 2-butoxyethanol as necessary. Examples thereof include those described in US Pat. Nos. 3,375,171 and 3,615,480.
Further, the developers described in JP-A-50-26601, 58-54341, JP-B-56-39464, and 56-42860 are also excellent.

In addition, as the plate-making process of the lithographic printing plate from the photopolymerizable lithographic printing plate of the present invention, the entire surface may be heated before exposure, during exposure, and between exposure and development, if necessary. By such heating, an image forming reaction in the photosensitive layer is promoted, and advantages such as improvement in sensitivity and printing durability and stabilization of sensitivity may occur. Further, for the purpose of improving the image strength and printing durability, it is also effective to carry out whole surface post-heating or whole surface exposure on the developed image. Usually, heating before development is preferably performed under mild conditions of 150 ° C. or less. Very strong conditions are used for heating after development. Usually, it is the range of 200-500 degreeC.
As the exposure method for the photopolymerizable lithographic printing plate of the present invention, a known method can be used without limitation. A laser is preferable as the light source. For example, the following can be used as an available laser light source having a wavelength of 350 to 450 nm.

Examples of the gas laser include Ar ion laser (364 nm, 351 nm, 10 mW to 1 W), Kr ion laser (356 nm, 351 nm, 10 mW to 1 W), and He—Cd laser (441 nm, 325 nm, 1 mW to 100 mW).
Examples of the solid-state laser include Nd: YAG (YVO ₄ ) and SHG crystal × 2 combinations (355 mm, 5 mW to 1 W), and Cr: LiSAF and SHG crystal (430 nm, 10 mW).
As a semiconductor laser system, KNbO ₃ , ring resonator (430 nm, 30 mW), waveguide type wavelength conversion element and AlGaAs, InGaAs semiconductor combination (380 nm to 450 nm, 5 mW to 100 mW), waveguide type wavelength conversion element and AlGaInP, Examples include combinations of AlGaAs semiconductors (300 nm to 350 nm, 5 mW to 100 mW), AlGaInN (350 nm to 450 nm, 5 mW to 30 mW), and the like.
In addition, examples of the pulse laser include N ₂ laser (337 nm, pulse 0.1 to 10 mJ), XeF (351 nm, pulse 10 to 250 mJ), and the like.
Among these, an AlGaInN semiconductor laser (commercially available InGaN-based semiconductor laser 400 to 410 nm, 5 to 30 mW) is particularly preferable in terms of wavelength characteristics and cost.

In addition, as an available light source of 450 nm to 700 nm, Ar ⁺ laser-(488 nm), YAG-SHG laser (532 nm), He-Ne laser (633 nm), He-Cd laser, red semiconductor laser (650-690 nm), Further, as an available light source of 700 nm to 1200 nm, a semiconductor laser (800 to 850 nm) and an Nd-YAG laser (1064 nm) can be preferably used.
Other ultra high pressure, high pressure, medium pressure, low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, ultraviolet laser lamps (ArF excimer laser, KrF excimer laser, etc.), radiation as electron beam, X Although a line, an ion beam, a far-infrared ray, etc. can be used, the above-mentioned laser light source of 350 nm or more is particularly preferable in terms of low cost.
The exposure mechanism may be any of an internal drum system, an external drum system, a flat bed system, and the like. The photosensitive layer component of the present invention can be made soluble in neutral water or weak alkaline water by using a highly water-soluble component. A lithographic printing plate having such a structure is placed on a printing machine. After loading, an exposure-development system can be performed on the machine.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.
[Examples 1 to 16, Comparative Examples 1 to 16]
(Preparation of support)
An aluminum plate having a thickness of 0.3 mm was etched by being immersed in 10% by mass sodium hydroxide at 60 ° C. for 25 seconds, washed with running water, neutralized with 20% by mass nitric acid, and then washed with water. This was subjected to an electrolytic surface roughening treatment in a 1% by mass nitric acid aqueous solution using a sinusoidal alternating waveform current at an anode time electricity of 300 coulomb / dm ² . Subsequently, after dipping in a 1% by mass aqueous sodium hydroxide solution at 40 ° C. for 5 seconds and then in a 30% by mass sulfuric acid aqueous solution and desmutting at 60 ° C. for 40 seconds, the current density in a 20% by mass sulfuric acid aqueous solution was 2A / current density. At dm ² , the anodization treatment was performed for 2 minutes so that the thickness of the anodized film was 2.7 g / m ² . When the surface roughness was measured, it was 0.3 μm (Ra display according to JIS B0601).

The following sol-gel reaction liquid was applied to the back surface of the substrate thus treated with a bar coater, dried at 100 ° C. for 1 minute, and a support provided with a backcoat layer having a coating amount after drying of 70 mg / m ^2. It was created.

Sol-gel reaction solution Tetraethyl silicate 50 parts by weight Water 20 parts by weight Methanol 15 parts by weight Phosphoric acid 0.05 parts by weight

  When the above components were mixed and stirred, heat generation started in about 5 minutes. After reacting for 60 minutes, a backcoat coating solution was prepared by adding the following solution.

Pyrogallol formaldehyde condensation resin (molecular weight 2000) 4 parts by weight dimethyl phthalate 5 parts by weight fluorinated surfactant (N-butylperfluorooctane 0.7 parts by weight sulfonamidoethyl acrylate / polyoxyethylene acrylate copolymer: molecular weight 20,000)
Methanol silica sol (manufactured by Nissan Chemical Industries, Ltd.,
Methanol 30% by mass) 50 parts by mass Methanol 800 parts by mass

(Preparation of photosensitive layer)
A photosensitive layer forming solution having the following composition was applied on the thus treated aluminum plate so that the dry coating amount was 1.3 g / m ² and dried at 100 ° C. for 1 minute to form a photosensitive layer.

(Photosensitive layer forming solution)
Photopolymerization initiator [X] Xg in Table 1 below
Sensitizing dyes [Y] Yg in Table 1 below
Polymer binder [Z] Zg shown in Table 1 below
The polymerizable compound [R] Rg in Table 1 below
Additives in the following Table-1 [S] Sg
Plasticizer [T] Tg in Table 1 below
Fluorosurfactant 0.06g
(Megafuck F-177: manufactured by Dainippon Ink & Chemicals, Inc.)
Thermal polymerization inhibitor 0.05g
(N-nitrosophenylhydroxylami aluminum salt)
Pigment dispersion 1.7 g
Composition of pigment dispersion
Pigment Blue 15: 6 15 parts by mass Allyl methacrylate / methacrylic acid copolymer 10 parts by mass (copolymerization molar ratio 83/17)
Cyclohexanone 15 parts by mass Methoxypropyl acetate 20 parts by mass Propylene glycol monomethyl ether 40 parts by mass Methyl ethyl ketone 29.5 g
Propylene glycol monomethyl ether 29.5 g

(Preparation of protective layer)
A 3% by weight aqueous solution of polyvinyl alcohol (saponification degree: 98 mol%, polymerization degree: 550) was applied on the above-mentioned photosensitive layer so that the dry coating weight was 2 g / m ² and dried at 100 ° C. for 2 minutes. Photopolymerizable lithographic printing plates (photosensitive materials) shown in Table 1 below were prepared.

  The activator compound [X], sensitizing dye [Y], binder polymer [Z], addition polymerizable compound [R], additive [S], and plasticizer [T] used in the photosensitive layer are shown below.

(Evaluation of sensitivity)
The light-sensitive material thus obtained was subjected to sensitivity evaluation using different light sources corresponding to the exposure wavelengths shown in Table 1 above. That is, using a 400 nm semiconductor laser, a 532 nm FD-YAG laser, and an 830 nm semiconductor laser, solid image exposure and halftone dot image exposure of 1 to 99% at 175 lines / inch in 1% increments were performed. Each exposed light-sensitive material was immersed in a developer having the following composition at 25 ° C. for 10 seconds, developed, and the sensitivity under each exposure condition was calculated in units of mJ / cm ² from the minimum exposure amount capable of forming an image. The smaller this value, the higher the sensitivity. However, if the light source wavelength is different, the amount of energy per photon is different. Therefore, even if it is simply considered, it is possible to sensitize even if the above-mentioned exposure amount is smaller as the wavelength becomes shorter. It becomes. Therefore, Table 3 below is meaningless for sensitivity comparison between different exposure conditions, and is intended only to see the difference between the example and the comparative example under the same exposure condition. The results are shown in Table 3 below.
(Developer composition)
0.2 g of aqueous potassium hydroxide solution having the following composition and pH of 12.0
1K potassium silicate 2.4g
(SiO ₂ / K ₂ O = 1.9)
The following compound A 5.0g
Ethylenediaminetetraacetic acid, 4Na salt 0.1g
91.3g of water

(Evaluation of storage stability)
The average value X _{0 of the} values obtained by measuring the halftone dot areas of the exposure settings 20%, 30%, 40%, and 50% on the printing plate shown in Table 1 on which the sensitivity evaluation was performed with the ccDOT manufactured by Centurfax 20%, 30%, 40%, 50% measured after the same printing plate was laser-exposed with the same amount of light as before high-temperature storage after being stored for 10 days under high temperature conditions (60 ° C). The difference (X ₀ −X ₁₀ ) in the average value X ₁₀ of the halftone dot area values was determined. The smaller this (X ₀ −X ₁₀ ) value, the better the storage stability, and it can be said that a storage stability of 5 or less is good.
An example of storage stability evaluation of the photosensitive material described in Example 1 is shown in Table 2 below.

Storage stability evaluation was similarly performed about Examples 2-16. Table 3 below shows the evaluation results and the evaluation results of Comparative Examples 1 to 16 when the plasticizer that is an essential component of the present invention was not added.

  From the above Table-3, it can be seen that the photopolymerizable lithographic printing plate of the present invention has high sensitivity and very good storage stability.

Claims (3)

An average value X _{10 of} 20%, 30%, 40%, and 50% halftone dot area measured after forced aging test stored at 60 ° C. for 10 days, and 20% measured before the forced aging test A planographic printing plate characterized in that the relationship between the average value X ₀ of halftone dot areas of 30%, 40%, and 50% is expressed by equation (1).
X ₀ (%) − 5 ≦ X ₁₀ (%) (1)   An activator compound that undergoes a chemical change by interaction with an electronically excited state generated by light absorption of (A) a sensitizing dye and (B) a sensitizing dye on a support, and (C) a radical. A lithographic printing plate comprising a photopolymerizable photosensitive layer containing an addition polymerizable compound that reacts with at least one of an acid and (D) a plasticizer. The lithographic printing plate according to claim 2, wherein the plasticizer is a compound having at least four ester groups.