JP2001125257A - Original plate for planographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a negative type photopolymerizable original plate for planographic pringing plate which has higher sensitivity due to the high adhesive strength of the photosensitive layer to the substrate, which is excellent also in printing durability and soiling property, which prevents skipping of thin lines and highlight even when ink on the plate surface is removed with a plate cleaner or printing is carried out in large quantities and in which direct laser beam writing is possible. SOLUTION: The original plate has a photopolymerizable photosensitive layer containing an alkali-soluble urethane binder having an ethylenically unsaturated polymerizable group in a side chain, a compound having an addition polymerizable ethylenically unsaturated double bond and a photopolymerization initiator on an aluminum substrate. The urethane binder is a reaction product of a diisocyanate compound and a diol compound having an ethylenically unsaturated polymerizable group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithographic printing plate precursor using a photopolymerizable composition. In particular, the present invention relates to a negative type lithographic printing plate precursor having high sensitivity to light rays in the visible light region and excellent mechanical strength, particularly excellent highlight characteristics.

[0002]

2. Description of the Related Art Conventionally, negative-working lithographic printing plate precursors are widely known, and include those having various photosensitive layers such as a diazo resin-containing type, a photopolymerization type, and a photocrosslinking type. In order to prepare a lithographic printing plate from such a lithographic printing plate precursor, it is common to place a transparent negative film original (lith film) on the photosensitive layer of these lithographic plates and image-expose using ultraviolet light. And the work was very time-consuming. In recent years, with the development of image forming technology, the use of a type of high-sensitivity photopolymerizable photosensitive layer suitable for non-contact type projection exposure plate making or visible light laser plate making, etc. Is scanned on the plate surface, and a character document, an image document, and the like are formed directly on the plate surface, and plate making can be performed directly without using a film document. However, conventional high-sensitivity photopolymerizable printing plates do not always have strong adhesion between the photosensitive layer and the support, so when used for high-volume printing at high speed,
The following problems occur: solid images are missing, and thin lines and highlights are skipped.

[0003] Further, when stains occur during printing, the plate surface is wiped with a plate cleaner on a printing press to remove ink.
If the adhesion between the photosensitive layer and the support was weak, there was a problem that the highlight portion would fly. Further, when the number of printed sheets is large, if the adhesion between the photosensitive layer and the support is weak, there is a problem that fine lines and highlight portions gradually fly as in the case where the plate surface is wiped with a plate cleaner.

However, there are strong demands in recent market trends, such as shortening the exposure time in order to improve productivity, and using the laser at a low output in order to extend the life of the laser.
Further increasing the sensitivity of lithographic printing plates that can be directly made is an eternal issue. However, even if the adhesive strength between the photosensitive layer and the support is sufficiently obtained, the plate surface is wiped with a plate cleaner or the like during printing, or even when printing hundreds of thousands of sheets, the tone reproduction is the same as the printed matter at the start, and An even more sensitive photopolymerizable lithographic printing plate without staining was in a very difficult situation.

Japanese Patent No. 2712564 describes that a photosensitive resin contains a polyurethane resin having an allyl group as a binder for the purpose of improving abrasion resistance and the like. However, this patent registration No. 27
Even if the technique described in JP-A-12564 is used, a lithographic printing plate precursor having sufficient characteristics could not be obtained.

[0006]

Therefore, according to the present invention, a high sensitivity and a high sensitivity can be obtained by the strong adhesion between the photosensitive layer and the support.
Negative photopolymerizable lithographic plate that excels in printing durability and stain resistance, does not fly fine lines and highlights even if a large amount of printing is performed even if ink on the plate surface is removed with a plate cleaner, and can be directly written by laser. The purpose is to provide a printing plate precursor.

[0007]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that at least a diisocyanate compound and a diol compound having an ethylenically unsaturated polymerizable group are reacted as a binder component of a photopolymerizable photosensitive layer. It has been found that the above object can be achieved by containing an alkali-soluble urethane binder obtained by the above, and the present invention has been accomplished. That is, the present invention comprises, on an aluminum support, an alkali-soluble urethane binder having an ethylenically unsaturated polymerizable group on a side chain, a compound having an addition-polymerizable ethylenically unsaturated double bond, and a photopolymerization initiator. A lithographic printing plate precursor comprising a photopolymerizable photosensitive layer, wherein the urethane binder is a reaction product of at least a diisocyanate compound and a diol compound having an ethylenically unsaturated polymerizable group.

The action mechanism of the lithographic printing plate precursor of the present invention is as follows.
Although it is not clear, the alkali-soluble urethane binder obtained by at least reacting the diisocyanate compound with the diol compound having an ethylenically unsaturated polymerizable group has an ethylenically unsaturated polymerizable group in the side chain, and the binder itself has a radical. It is considered that the polymerization reaction causes the image portion of the photopolymerizable photosensitive layer to form a denser crosslinked structure. According to the technique described in Japanese Patent No. 2712564, the radical polymerization reaction does not occur because the group in the side chain of the urethane binder is an allyl group, and the image portion of the photosensitive layer forms a sufficiently dense crosslinked structure. Never.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a lithographic printing plate precursor according to the present invention will be described in detail. (Alkali-soluble urethane binder) First, is the most important element in the lithographic printing plate precursor of the present invention,
The alkali-soluble urethane binder will be described.
The alkali-soluble urethane binder contained in the photopolymerizable photosensitive layer of the lithographic printing plate precursor according to the invention is obtained by at least reacting a diisocyanate compound with a diol compound having at least one ethylenically unsaturated polymerizable group. Having at least one ethylenically unsaturated polymerizable group in the side chain.

A) Diisocyanate compound The diisocyanate compound used for obtaining the alkali-soluble urethane binder is not particularly limited, and examples thereof include those represented by the following general formula (1).

OCN-L ¹ -NCO General formula (1)

In the formula, L ¹ represents an optionally substituted 2
And a monovalent aliphatic or aromatic hydrocarbon group. If necessary, L ¹ may have another functional group that does not react with the isocyanate group, for example, an ester, urethane, amide, or ureido group. Specific examples of the diisocyanate compound represented by the general formula (1) include the following. That is, 2,4-tolylene diisocyanate,
2,4-tolylene diisocyanate dimer, 2,6-
Tolylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 4,
Aromatic diisocyanate compounds such as 4'-diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate; hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer Aliphatic diisocyanate compounds such as acid diisocyanate; isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4
(Or 2,6) an alicyclic diisocyanate compound such as diisocyanate, 1,3- (isocyanatomethyl) cyclohexane and the like; a diol such as an adduct of 1 mol of 1,3-butylene glycol and 2 mol of tolylene diisocyanate And a diisocyanate compound which is a reaction product of diisocyanate.

B) Diol compound The diol compound used for obtaining the alkali-soluble urethane binder has at least one ethylenically unsaturated polymerizable group (hereinafter simply referred to as an unsaturated group) in a side chain. There is no particular limitation as long as it exists. As such a diol compound having an unsaturated group, for example, in addition to using a commercially available one such as trimethylol monoallyl ether, a halogenated diol compound, a triol compound, an amino diol compound and an unsaturated diol compound having an unsaturated group Examples include compounds that can be easily produced by reaction with carboxylic acids, acid chlorides, isocyanates, alcohols, amines, thiols, and alkyl halide compounds. Specific examples of these compounds include the following compounds, but are not limited thereto.

[0014]

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[0015]

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[0016]

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[0017]

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[0018]

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Further, in order to obtain the alkali-soluble urethane binder, a diol compound other than the diol compound having an unsaturated group, in addition to the diisocyanate compound and the diol compound having an unsaturated group, can be used for the formation reaction. Examples of the diol compound other than the diol compound having an unsaturated group include, but are not particularly limited to, those represented by the following general formula (2).

HO-Y ⁰ -OH General formula (2)

(In the formula, Y ⁰ represents a divalent organic residue.) The diol compound represented by the general formula (2) is not particularly limited, and examples thereof include a polyether diol compound and a polyester diol. And polycarbonate diol compounds. As the polyether diol compound, general formulas (3), (4),
Compounds represented by (5), (6), and (7), and random copolymers of ethylene oxide and propylene oxide each having a hydroxyl group at a terminal are exemplified.

[0022]

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In the formula, R ¹ is a hydrogen atom or a methyl group, X
Represents the following groups.

[0024]

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A, b, c, d, e, f and g are each 2
The following integers are shown. Preferably it is an integer of 2 to 100.

Specific examples of the polyether diol compounds represented by the general formulas (3) and (4) include the following. That is, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, heptaethylene glycol, octaethylene glycol,
Di-1,2-propylene glycol, tri-1,2-propylene glycol, tetra-1,2-propylene glycol, hexa-1,2-propylene glycol, di-
1,3-propylene glycol, tri-1,3-propylene glycol, tetra-1,3-propylene glycol, di-1,3-butylene glycol, tri-1,3-
Butylene glycol, hexa-1,3-butylene glycol, polyethylene glycol having a weight average molecular weight of 1,000, polyethylene glycol having a weight average molecular weight of 1500, polyethylene glycol having a weight average molecular weight of 2,000, polyethylene glycol having a weight average molecular weight of 3,000, and polyethylene having a weight average molecular weight of 7,500 Glycol, polypropylene glycol having a weight average molecular weight of 400, polypropylene glycol having a weight average molecular weight of 700, polypropylene glycol having a weight average molecular weight of 1,000, polypropylene glycol having a weight average molecular weight of 2,000, polypropylene glycol having a weight average molecular weight of 3,000, polypropylene glycol having a weight average molecular weight of 4,000, etc. .

Specific examples of the polyether diol compound represented by the formula (5) include the following. Sanyo Kasei Kogyo Co., Ltd. PTMG650, PTM
G1000, PTMG2000, PTMG3000 and the like.
Specific examples of the polyether diol compound represented by the general formula (6) include the following. New Pole PE-61, New Pole PE-62, New Pole PE-64, New Pole PE-68, New Pole PE-71, New Pole P manufactured by Sanyo Chemical Industry Co., Ltd.
E-74, New Pole PE-75, New Pole PE
-78, New Pole PE-108, New Pole PE
-128, New Pole PE-61 and the like.

Specific examples of the polyether diol compound represented by the general formula (7) include the following. New pole BPE-2 manufactured by Sanyo Chemical Industry Co., Ltd.
0, Newpole BPE-20F, Newpole BPE
-20NK, New Pole BPE-20T, New Pole BPE-20G, New Pole BPE-40, New Pole BPE-60, New Pole BPE-100, New Pole BPE-180, New Pole BPE-2
P, New Pole BPE-23P, New Pole BPE
-3P, Newpole BPE-5P and the like.

Specific examples of the random copolymer of ethylene oxide and propylene oxide having a hydroxyl group at the terminal include the following. New Pole 50HB-100, New Pole 50HB-260, New Pole 50HB-400, New Pole 50HB-660, New Pole 50HB- manufactured by Sanyo Chemical Industries, Ltd.
2000, Newpole 50HB-5100, etc.

Examples of the polyester diol compound include compounds represented by formulas (8) and (9).

[0031]

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In the formula, L ¹ , L ² and L ³ may be the same or different and each represents a divalent aliphatic or aromatic hydrocarbon group, and L ⁴ represents a divalent aliphatic hydrocarbon group. . Preferably, L ¹ , L ² and L ³ each represent an alkylene group, alkenylene group, alkynylene group or arylene group;
⁴ represents an alkylene group. In L ¹ , L ² , L ³ and L ⁴ , other functional groups which do not react with an isocyanate group, such as ether, carbonyl, ester, cyano, olefin,
Urethane, amide, ureido groups or halogen atoms may be present. n1 and n2 are each an integer of 2 or more, and preferably an integer of 2 to 100.

As the polycarbonate diol compound, there is a compound represented by the general formula (10).

[0034]

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In the formula, L ⁵ may be the same or different, and represents a divalent aliphatic or aromatic hydrocarbon group. Preferably, L ⁵ represents an alkylene, alkenylene, alkynylene, or arylene group. The other functional group which does not react with an isocyanate group L ^5, such as ethers,
A carbonyl, ester, cyano, olefin, urethane, amide, ureido group or halogen atom may be present. n3 is an integer of 2 or more, and preferably an integer of 2 to 100.

The diol compounds represented by the general formulas (8), (9) and (10) specifically include the following. N in a specific example is an integer of 2 or more.

[0037]

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[0038]

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[0039]

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[0040]

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The polyurethane resin used in the present invention is:
More preferably, it is a polyurethane resin having a carboxyl group. The polyurethane resin which is preferably used is obtained by opening a structural unit represented by at least one of diol compounds of the general formulas (11), (12) and (13) and / or tetracarboxylic dianhydride with a diol compound. A polyurethane resin having a structural unit derived from a cyclic compound.

[0042]

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R ² is a hydrogen atom, a substituent (eg, cyano, nitro, halogen atom, (—F, —Cl, —Br,
_{-I), - CONH 2, -COOR} 3, -OR 3, -NH
CONHR ³ , —NHCOOR ³ , —NHCOR ³ , —O
CONHR ³ (where R ³ represents an alkyl group having 1 to 10 carbon atoms and an aralkyl group having 7 to 15 carbon atoms). Represents an alkyl, aralkyl, aryl, alkoxy, aryloxy group which may have
It preferably represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 15 carbon atoms. L ⁶ , L ⁷ , and L ⁸ may be the same or different, and may have a single bond or a substituent (for example, each group of alkyl, aralkyl, aryl, alkoxy, and halogeno is preferable). It represents a divalent aliphatic or aromatic hydrocarbon group. It preferably represents an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 15 carbon atoms, and more preferably an alkylene group having 1 to 8 carbon atoms. If necessary, L ⁶ , L ⁷ , and L ⁸ may have other functional groups that do not react with an isocyanate group, such as carbonyl, ester, urethane, amide, ureide, and ether groups. Note that R ² , L ⁶ , L ⁷ , L ⁸
And two or three of them may form a ring.

Ar represents a trivalent aromatic hydrocarbon group which may have a substituent, preferably an aromatic group having 6 to 15 carbon atoms.

C) Carboxyl-Containing Diol Compound The carboxyl-containing diol compound represented by the general formula (11), (12) or (13) specifically includes the following compounds. That is, 3,5-dihydroxybenzoic acid, 2,2-bis (hydroxymethyl)
Propionic acid, 2,2-bis (2-hydroxyethyl)
Propionic acid, 2,2-bis (3-hydroxypropyl) propionic acid, bis (hydroxymethyl) acetic acid, bis (4-hydroxyphenyl) acetic acid, 2,2-bis (hydroxymethyl) butyric acid, 4,4-bis ( 4-hydroxyphenyl) pentanoic acid, tartaric acid, N, N-dihydroxyethylglycine, N, N-bis (2-hydroxyethyl) -3-carboxy-propionamide and the like.

In the present invention, preferred tetracarboxylic dianhydrides used for synthesizing the polyurethane resin include those represented by formulas (14), (15) and (16).

[0047]

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In the formula, L ⁹ is a single bond, a substituent (eg, alkyl, aralkyl, aryl, alkoxy, halogeno,
Ester and amide groups are preferred. ) May have a divalent aliphatic or aromatic hydrocarbon group, -CO-,
_{-SO -, - SO 2 -,} - indicating O- or -S-. Preferably a single bond, the number 1-15 divalent aliphatic hydrocarbon group having a _{carbon, -CO -, - SO 2 -} , - indicating O- or -S-. R ⁴ and R ⁵ may be the same or different and represent a hydrogen atom, an alkyl, an aralkyl, an aryl, an alkoxy, or a halogeno group. Preferably, it represents a hydrogen atom, an alkyl having 1 to 8 carbons, an aryl having 6 to 15 carbons, an alkoxy having 1 to 8 carbons, or a halogeno group.
Also, two of L ⁹ , R ⁴ and R ⁵ may combine to form a ring. R ⁶ and R ⁷ may be the same or different and represent a hydrogen atom, an alkyl, an aralkyl, an aryl or a halogeno group. It preferably represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 15 carbon atoms. Also, two of L ⁹ , R ⁶ and R ⁷ may combine to form a ring. L ¹⁰ and L ¹¹ may be the same or different and represent a single bond, a double bond, or a divalent aliphatic hydrocarbon group. It preferably represents a single bond, a double bond, or a methylene group. A represents a mononuclear or polynuclear aromatic ring. It preferably represents an aromatic ring having 6 to 18 carbon atoms.

Formula (14), (15) or (16)
Specific examples of the compound represented by the following include those shown below. That is, pyromellitic dianhydride, 3,
3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyltetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 4,4'-sulfonyldiphthalic dianhydride, 2,2-bis (3,4-dicarboxyphenyl)
Propane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 4,4 ′-[3,3 ′-(alkylphosphoryldiphenylene) -bis (iminocarbonyl)] diphthalic dianhydride, Aromatic tetracarboxylic dianhydrides such as adducts of hydroquinone diacetate and trimetic anhydride, and adducts of diacetyldiamine and trimetic anhydride; 5- (2,5-dioxotetrahydrofuryl) -3-methyl- 3-cyclohexene-1,2-dicarboxylic anhydride (Epiclon B-4400, manufactured by Dainippon Ink and Chemicals, Incorporated), 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,2 Alicyclic tetracarboxylic dianhydrides such as 4,5-cyclohexanetetracarboxylic dianhydride and tetrahydrofurantetracarboxylic dianhydride; 1 2,3,4 butane tetracarboxylic acid dianhydride, 1,2,4,5-aliphatic tetracarboxylic dianhydrides such as pentane tetracarboxylic acid dianhydride.

As a method for introducing a structural unit derived from a compound obtained by ring-opening these tetracarboxylic dianhydrides with a diol compound, for example, the following method is available. a) A method in which an alcohol-terminated compound obtained by ring-opening a tetracarboxylic dianhydride with a diol compound is reacted with a diisocyanate compound. b) A method in which a diisocyanate compound is reacted under the condition of an excess of a diol compound to react an alcohol-terminated urethane compound obtained with tetracarboxylic dianhydride.

The diol compound used at this time specifically includes the following compounds. That is, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, 1,3-butylene glycol, 1,6
-Hexanediol, 2-butene-1,4-diol,
2,2,4-trimethyl-1,3-pentanediol,
1,4-bis-β-hydroxyethoxycyclohexane, cyclohexanedimethanol, tricyclodecanedimethanol, hydrogenated bisphenol A, hydrogenated bisphenol F, ethylene oxide adduct of bisphenol A,
Propylene oxide adduct of bisphenol A, ethylene oxide adduct of bisphenol F, propylene oxide adduct of bisphenol F, ethylene oxide adduct of hydrogenated bisphenol A, propylene oxide adduct of hydrogenated bisphenol A, hydroquinone dihydroxyethyl ether, p -Xylylene glycol,
Dihydroxyethyl sulfone, bis (2-hydroxyethyl) -2,4-tolylenedicarbamate, 2,4-tolylene-bis (2-hydroxyethylcarbamide), bis (2-hydroxyethyl) -m-xylylenedicarbamate, bis (2-hydroxyethyl) isophthalate and the like.

D) Other diol compounds Further, a diol compound which does not have a carboxyl group and may have another substituent which does not react with isocyanate can be used in combination. Such diol compounds include those shown below.

HO-L ¹³ -O-CO-L ¹⁴ -CO-OL ¹³ -OH Formula (17) HO-L ¹⁴ -CO-OL ¹³ -OH Formula (18)

In the formula, L ¹³ and L ¹⁴ may be the same or different and each has a substituent (for example, alkyl, aralkyl, aryl, alkoxy, aryloxy, halogen atom (-F, -Cl, -Br,- A) a divalent aliphatic hydrocarbon group which may have:
It represents an aromatic hydrocarbon group or a heterocyclic group. As needed,
Other functional groups which do not react with an isocyanate group in L ¹³ and L ¹⁴ , such as carbonyl, ester, urethane, amide,
It may have a ureido group or the like. L ¹³ and L ¹⁴ may form a ring.

Further, specific examples of the compound represented by the general formula (17) or (18) include the following.

[0056]

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[0057]

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[0058]

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[0059]

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The following diol compounds can also be suitably used.

[0061]

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In the general formula, R ⁸ and R ⁹ may be the same or different, and may have an optionally substituted alkyl group c.
Has the same meaning as described above and represents an integer of 2 or more, preferably 2
It is an integer of １００100. Specific examples of the diol compounds represented by the general formulas (19) and (20) include the following. That is, as the general formula (19), ethylene glycol, 1,3-propanediol,
1,4-butanediol, 1,5-pentanediol,
Examples of the general formula (20) such as 1,6-hexanediol, 1,7-heptanediol, and 1,8-octanediol include compounds shown below.

[0063]

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Also, the following diol compounds can be suitably used.

HO-L ¹⁵ -NH-CO-L ¹⁶ -CO-NH-L ¹⁵ -OH Formula (21) HO-L ¹⁶ -CO-NH-L ¹⁵ -OH Formula (22)

In the formula, L ¹⁵ and L ¹⁶ may be the same or different and each has a substituent (eg, alkyl, aralkyl, aryl, alkoxy, aryloxy, halogen atom (—F, —Cl, —Br, — A) a divalent aliphatic hydrocarbon group which may have:
It represents an aromatic hydrocarbon group or a heterocyclic group. As needed,
Other functional groups which do not react with isocyanate groups in L ¹⁵ and L ¹⁶ , such as carbonyl, ester, urethane, amide,
It may have a ureido group or the like. L ¹⁵ and L ¹⁶ may form a ring.

Further, specific examples of the compound represented by the general formula (21) or (22) include the following.

[0068]

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[0069]

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Further, the following diol compounds can also be suitably used. ^{HO-Ar 2 - (L 17} -Ar 3) n-OH Formula ^{(23) HO-Ar 2 -L} 17 -OH Formula (24)

In the formula, L ¹⁷ is a substituent (eg, alkyl,
Aralkyl, aryl, alkoxy, aryloxy and halogeno groups are preferred. ) Represents a divalent aliphatic hydrocarbon group which may have If necessary, other functional groups which do not react with isocyanate groups in L ¹⁷ , such as esters,
It may have a urethane, amide, or ureido group. A
r ² and Ar ³ may be the same or different, and represent a divalent aromatic hydrocarbon group which may have a substituent, and preferably represents an aromatic group having 6 to 15 carbon atoms. n is 0 to 10
Indicates an integer.

The diol compound represented by the general formula (23) or (24) specifically includes the following. That is, catechol, resorcin, hydroquinone, 4-methylcatechol, 4-t-butylcatechol, 4-acetylcatechol, 3-methoxycatechol, 4-phenylcatechol, 4-methylresorcin, 4-ethylresorcin, 4-t-butyl Resorcinol, 4-hexylresorcinol, 4-chlororesorcinol,
4-benzyl resorcinol, 4-acetyl resorcinol, 4
-Carbomethoxy resorcin, 2-methyl resorcin,
5-methylresorcinol, t-butylhydroquinone,
2,5-di-t-butylhydroquinone, 2,5-di-
t-amylhydroquinone, tetramethylhydroquinone, tetrachlorohydroquinone, methylcarbaminohydroquinone, methylureidohydroquinone, methylthiohydroquinone, benzonorbornene-3,6-
Diol, bisphenol A, busphenol S, 3,
3'-dichlorobisphenol S, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxybiphenyl, 4,4'-thiodiphenol, 2,2'-dihydroxydiphenylmethane, 3,4-bis (p-hydroxyphenyl ) Hexane, 1,4-bis (2- (p-hydroxyphenyl) propyl) benzene, bis (4-hydroxyphenyl) methylamine, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-
Dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 1,5-dihydroxyanthraquinone, 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, 2-hydroxy-3,5-di-t-butylbenzyl alcohol, 4-hydroxy-3 , 5-di-t-
Butylbenzyl alcohol, 4-hydroxyphenethyl alcohol, 2-hydroxyethyl-4-hydroxybenzoate, 2-hydroxyethyl-4-hydroxyphenyl acetate, resorcinol mono-2-hydroxyethyl ether and the like. The following diol compounds can also be suitably used.

[0073]

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Where R^TenIs a hydrogen atom, a substituent (for example,
Cyano, nitro, halogen atom (-F, -Cl, -B
r, -I), -CONH_Two, -COOR¹¹, -OR¹¹,
-NHCONHR¹¹, -NHCOOR¹¹, -NHCOR
¹¹, -OCONHR¹¹, -CONHR¹¹(Where R¹¹
Represents an alkyl group having 1 to 10 carbon atoms and an ara group having 7 to 15 carbon atoms.
Represents a alkyl group. )). )
Alkyl, aralkyl, aryl, alkoxy
Represents an aryloxy group, preferably a hydrogen atom, carbon
An alkyl group having 1 to 8 carbon atoms and an aryl having 6 to 15 carbon atoms
Represents a group. L¹⁸, L¹⁹, L²⁰Are the same but different
May be a single bond, a substituent (eg, alkyl,
Aralkyl, aryl, alkoxy, and halogen groups are preferred.
Good. Divalent aliphatic or aromatic optionally having
Represents a group hydrocarbon group. Preferably, it has 1 to 20 carbon atoms.
Alkylene group, arylene group having 6 to 15 carbon atoms, and
It preferably represents an alkylene group having 1 to 8 carbon atoms. necessary
Depending on¹⁸, L¹⁹, L²⁰Isocyanate groups
Other functional groups that do not respond, such as carbonyl, ester,
Even if it has a urethane, amide, ureide or ether group
Good. Note that R^Ten, L ¹⁸, L¹⁹, L²⁰2 of or
Three may form a ring.

Ar represents a trivalent aromatic hydrocarbon group which may have a substituent, preferably an aromatic group having 6 to 15 carbon atoms. Z ₀ represents the following groups.

[0076]

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Here, R ¹² and R ¹³ may be the same or different, and each represents a hydrogen atom, sodium, potassium,
Represents an alkyl group or an aryl group, preferably a hydrogen atom,
An alkyl group having 1 to 8 carbon atoms and an aryl group having 6 to 15 carbon atoms are shown.

Formula (25), (26) or (27)
The diol compound having a phosphonic acid, a phosphoric acid and / or an ester group thereof represented by is synthesized by, for example, the following method. The following general formulas (28) and (2)
9) After protecting the hydroxy group of the halogen compound represented by (30) as necessary, the compound represented by the formula (31)
The synthesis is carried out by phosphonate esterification by a chaelis-Arbuzov reaction and, if necessary, hydrolysis with hydrogen bromide or the like.

[0079]

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Wherein R ¹⁰ , L ¹⁸ , L ¹⁹ , L ²⁰ and Ar
Is the same as in the case of the equations (25), (26) and (27). R ¹⁴ represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 15 carbon atoms. R ¹⁵ is represented by the formulas (28), (29) and (30)
A residue obtained by removing X ¹ of, X ¹ is a halogen atom, preferably denotes Cl, Br, and I. After the reaction with phosphorus oxychloride represented by the general formula (32), the synthesis is carried out by a hydrolysis method.

[0081]

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In the formula, R ¹⁵ has the same meaning as in formula (31), and M represents a hydrogen atom, sodium or potassium.
When the polyurethane resin of the present invention has a phosphonic acid group, the diisocyanate compound represented by the general formula (1) and the diol compound having an unsaturated group are represented by the general formula (25), (26) or (27). The diol compound having a phosphonate ester group may be reacted to form a polyurethane resin, and then hydrolyzed with hydrogen bromide or the like.

Further, since the urethane binder of the present invention needs to be alkali-soluble, it is necessary to impart alkali solubility during or after the production thereof. The alkali solubility is imparted during the production rather than after the production of the urethane binder of the present invention, so that the process can be simplified, and there is little reaction debris that affects printing performance such as ease of production and sensitivity. Preferred for that reason. The method of imparting alkali solubility during the production of the urethane binder of the present invention is not particularly limited,
For example, a method of introducing an alkali-soluble group into the side chain of the urethane binder is mentioned. More specifically, it is preferable to use a diisocyanate compound or a diol compound having an alkali-soluble group, and particularly to use a diol compound having an alkali-soluble group. Preferably, it is used.

The alkali-soluble group is not particularly limited, and examples thereof include a carboxyl group, a sulfonamide group, a phenolic hydroxyl group, and the like. A carboxyl group is particularly preferable in terms of excellent alkali solubility. Also,
Examples of the diol compound having a carboxyl group include those described above.

Further, the following amino group-containing compounds may be reacted with the diisocyanate compound and the diol compound to form a urea structure and be incorporated into the structure of the polyurethane resin binder.

[0086]

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(Wherein R ¹⁶ and R ¹⁷ may be the same or different, and each represents a hydrogen atom, a substituent (eg, alkoxy, a halogen atom (—F, —Cl, —Br, —I), an ester, An alkyl, aralkyl, or aryl group which may have a hydrogen atom, and preferably has 1 to 8 carbon atoms which may have a carboxyl group as a substituent. L ²¹ represents a substituent (for example, alkyl, aralkyl, aryl, alkoxy, aryloxy, halogen atom (-F, -Cl, -Br,-
I) and carboxyl groups. A) a divalent aliphatic hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic group which may have If necessary, L ²¹ may have another functional group which does not react with an isocyanate group, for example, a carbonyl, ester, urethane, amide group and the like. Note that two of R ¹⁶ , L ²¹ and R ¹⁷ may form a ring.

Specific examples of the compounds represented by formulas (33) and (34) include the following.
That is, ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, dodecamethylenediamine, propane-1,2-diamine, bis (3-aminopropyl) methylamine, , 3-Bis (3-aminopropyl) tetramethylsiloxane, piperazine, 2,5-dimethylpiperazine, N- (2-aminoethyl) piperazine, 4-amino-2,2-6,6-tetramethylpiperidine, N ,
Aliphatic diamine compounds such as N-dimethylethylenediamine, lysine, L-cystine, isophoronediamine; o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,4-tolylenediamine, benzidine, o-ditoluidine , O-dianisidine, 4-nitro-m-phenylenediamine, 2,5-dimethoxy-p-phenylenediamine, bis- (4-aminophenyl) sulfone, 4-carboxy-o-phenylenediamine, 3-carboxy-m- Aromatic diamine compounds such as phenylenediamine, 4,4'-diaminophenyl ether, 1,8-naphthalenediamine and the like; 2
-Aminoimidazole, 3-aminotriazole, 5-
Amino-1H-tetrazole, 4-aminopyrazole,
Such as 2-aminobenzimidazole, 2-amino-5-carboxy-triazole, 2,4-diamino-6-methyl-S-triazine, 2,6-diaminopyridine, L-histidine, DL-tryptophan, adenine and the like Heterocyclic amine compound; ethanolamine, N-methylethanolamine, N-ethylethanolamine, 1-amino-2-propanol, 1-amino-3-propanol, 2-aminoethoxyethanol, 2-aminothioethoxyethanol, 2 -Amino-2-methyl-1-propanol, p-aminophenol, m-aminophenol, o-aminophenol, 4-methyl-2-aminophenol, 2-chloro-4-aminophenol, 4-methoxy-3- Aminophenol, 4-hydroxybenzylamine, 4-a Bruno-1-naphthol, 4-aminosalicylic acid, 4-hydroxy -N- phenylglycine, 2
-Amino alcohols or aminophenol compounds such as aminobenzyl alcohol, 4-aminophenethyl alcohol, 2-carboxy-5-amino-1-naphthol, L-tyrosine and the like.

The polyurethane resin of the present invention is synthesized by adding the above-mentioned diisocyanate compound and diol compound in an aprotic solvent to a known catalyst having an activity corresponding to the respective reactivity, and heating. The molar ratio of the diisocyanate and the diol compound used is preferably 0.8: 1 to 1.2: 1. When the isocyanate group remains at the polymer terminal, the polymer is treated with alcohols or amines to obtain the final Is synthesized in such a manner that no isocyanate group remains.

The polyurethane resin of the present invention is preferably a polyurethane resin having a structure represented by a reaction product with at least one of a polyether diol compound, a polyester diol compound, and a polycarbonate diol compound. The content in the resin is preferably 1 to 80% by weight, more preferably 5 to 60% by weight. The polyurethane resin of the present invention preferably contains an aromatic group in a main chain and / or a side chain. More preferably, the content of the aromatic group in the polyurethane resin is 1
It is in the range of 0 to 80% by weight. The polyurethane resin of the present invention is preferably a polyurethane resin having a carboxyl group.
It is preferably contained in an amount of 4 meq / g or more, more preferably in the range of 0.4 to 3.5 meq / g. The molecular weight of the polyurethane resin of the present invention is preferably at least 1,000 by weight, more preferably 10,000.
It is in the range of 300,000.

[Addition-Polymerizable Compound] Next, a compound having an addition-polymerizable ethylenically unsaturated double bond contained in the photopolymerizable photosensitive layer of the lithographic printing plate precursor according to the invention (hereinafter simply referred to as addition (Also referred to as a polymerizable compound).
The addition-polymerizable compound used in the present invention is not particularly limited as long as it is a compound having an addition-polymerizable ethylenically unsaturated double bond, but preferably has at least one terminal ethylenically unsaturated bond, more preferably It is selected from compounds having two or more. Such compounds are widely known in the industrial field, and they can be used in the invention without any particular limitation. These have chemical forms such as, for example, monomers, prepolymers, ie, dimers, trimers and oligomers, or mixtures thereof and copolymers thereof. Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example,
Acrylic acid, methacrylic acid, itaconic acid, crotonic acid,
Isocrotonic acid, maleic acid, etc.), esters and amides thereof, preferably esters of unsaturated carboxylic acids with aliphatic polyhydric alcohol compounds, and unsaturated carboxylic acids with aliphatic polyhydric amine compounds. Amides are used. Further, an unsaturated carboxylic acid ester having a nucleophilic substituent such as a hydroxyl group, an amino group or a mercapto group, an addition reaction product of an amide with a monofunctional or polyfunctional isocyanate, an epoxy, a monofunctional or A dehydration-condensation reaction product with a functional carboxylic acid is also preferably used. Further, an isocyanate group or an unsaturated carboxylic acid ester having an electrophilic substituent such as an epoxy group, an addition reaction product of an amide with a monofunctional or polyfunctional alcohol, an amine, or a thiol, a halogen group, Having a leaving substituent such as a tosyloxy group, an unsaturated carboxylic acid ester, an amide and a monofunctional or polyfunctional alcohol,
Substituted reactants with amines and thiols are also suitable. As another example, it is also possible to use a group of compounds in which unsaturated phosphonic acid, styrene, vinyl ether or the like is substituted for the above unsaturated carboxylic acid.

Particularly preferred addition-polymerizable compounds are urethane-based addition-polymerizable compounds produced by an addition reaction between an isocyanate and a hydroxyl group. As a specific example, for example, a hydroxyl group represented by the following general formula (35) is added to a polyisocyanate compound having two or more isocyanate groups in one molecule described in JP-B-48-41708. 1 with added vinyl monomer
A vinyl urethane compound containing two or more polymerizable vinyl groups in the molecule is exemplified.

CH ₂ CC (R) COOCH ₂ CH (R ′) OH Formula (35) (where R and R ′ represent H or CH ₃ )

Further, urethane (meth) acrylates described in JP-A-51-37193, JP-B-2-32293 and JP-B-2-16765, and JP-B-58-49860 and JP-B-58-49860. Examples thereof include urethane compounds having an ethylene oxide skeleton described in JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418. Particularly preferred specific examples include the following compounds. It is a reaction product of a polyisocyanate compound of the following (1) group and an alcohol compound of the (2) group.

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[0096]

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[0097]

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[0098]

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[0099]

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More specifically, the following compounds correspond to them. Urethane acrylate M- manufactured by Toa Gosei Co., Ltd.
1100, M-1200, M-1210, M-130
0, urethane acrylate EB210, EB4827, EB6700, EB manufactured by Daicel UCB Co., Ltd.
220, MORTON THIOKOL Inc. U
VITHANE-782, UVITHANE-783,
UVITHANE-788, UVITHANE-89
3. Art resin UN-9000E manufactured by Negami Industry Co., Ltd.
P, Art Resin UN-9200A, Art Resin UN
-9000H, Art Resin UN-1255, Art Resin UN-5000, Art Resin UN-2111A,
Art Resin UN-2500, Art Resin UN-33
20HA, Art resin UN-3320HB, Art resin UN-3320HC, Art resin UN-3320
HS, Art Resin UN-6060P, Art Resin U
N-6060PTM, Art Resin SH-380G, Art Resin SH-500, Art Resin SH-983
2. NK Oligo U-4H, NK Oligo U-4HA, NK Oligo U-4P, NK Oligo U- manufactured by Shin-Nakamura Chemical Co., Ltd.
4PA, NK Oligo U-4TX, NK Oligo U-4TX
A, NK oligo U-6LHA, NK oligo U-6LPA
-N, NK oligo U-6LTXA, NK oligo UA-6
ELP, NK oligo UA-6 ELH, NK oligo UA-
6ELTX, NK oligo UA-6PLP, NK oligo U
-6ELP, NK oligo U-6ELH, NK oligo U-
8MDA, NK Oligo U-8MD, NK Oligo U-12
LMA, NK oligo U-12LM, NK oligo U-6H
A, NK oligo U-108A, NK oligo U-1084
A, NK oligo U-200AX, NK oligo U-122
A, NK oligo U-340A, NK oligo U-324
A, NK Oligo UA-100, A manufactured by Kyoeisha Chemical Co., Ltd.
H-600, AT-600, UA-306H, AI-6
00, UA-101T, UA-101I, UA-101
H, UA-306T, UA-306I, UF-800
1, UF-8003 and the like.

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

Examples of methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, and 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-hi Rokishipuropokishi) phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

Examples of itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate,
There are 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, sorbitol tetritaconate and the like. Crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, sorbitol tetradicrotonate and the like. Examples of the isocrotonic acid ester include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.

The maleic acid ester includes ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, sorbitol tetramaleate and the like. Examples of other esters include:
For example, JP-B-46-27926, JP-B-51-473.
34, aliphatic alcohol esters described in JP-A-57-196231, JP-A-59-5240 and JP-A-59-196231.
No. 5,241, those having an aromatic skeleton described in JP-A-2-226149 and those containing an amino group described in JP-A-1-165613 are also suitably used. Further, the above-mentioned ester monomers can be used as a mixture.

Specific examples of the amide monomer of the aliphatic polyamine compound and the unsaturated carboxylic acid include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6- Hexamethylene bis-methacrylamide,
Examples include diethylenetriaminetrisacrylamide, xylylenebisacrylamide, xylylenebismethacrylamide, and the like. Examples of other preferred amide monomers include those having a cyclohexylene structure described in JP-B-54-21726. Further, JP-A-63-277653, JP-A-63-260909,
By using an addition polymerizable compound having an amino structure or a sulfide structure in the molecule described in JP-A-1-105238, a photopolymerizable composition having a very high photosensitive speed can be obtained.

As another example, see JP-A-48-641.
No. 83, JP-B-49-43191, JP-B-52-30
No. 490, and polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates obtained by reacting an epoxy resin with (meth) acrylic acid as described in each publication. Also,
JP-B-46-43946, JP-B-1-40337,
Specific unsaturated compounds described in JP-B-1-40336,
Vinyl phosphonic acid compounds described in JP-A-2-25493 can also be mentioned. In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Japan Adhesion Association Journal vol. 20, No. 7, pages 300-308 (198
(4 years) as photocurable monomers and oligomers can also be used.

Regarding the addition polymerizable compound, what kind of structure is used, whether it is used alone or in combination,
Details of the method of use, such as the amount of addition, can be arbitrarily set according to the performance design of the final lithographic printing plate precursor. For example, it is selected from the following viewpoints. A structure having a large content of unsaturated groups per molecule is preferable from the viewpoint of the photosensitive speed, and in many cases, a bifunctional or more functional structure is preferable. Also, in order to increase the strength of the image area, that is, the cured film,
A compound having three or more functional groups is preferred. Furthermore, by using a combination of different functional groups and different polymerizable groups (for example, acrylic ester, methacrylic ester, styrene-based compound, and vinyl ether-based compound), photosensitivity and strength can be improved. A method of adjusting both is also effective. Large molecular weight compounds,
A compound having high hydrophobicity is excellent in photosensitive speed and film strength, but may not be preferable in terms of developing speed and precipitation in a developing solution. Further, other components in the photosensitive layer (for example, a binder, a titanocene compound (photopolymerization initiator),
The selection and use of the addition-polymerizable compound is also an important factor for the compatibility and dispersibility with the colorant, etc., for example, by using a low-purity compound or by using two or more compounds in combination. Can be improved. In addition, a specific structure may be selected for the purpose of improving the adhesion of a support, an overcoat layer, and the like described below. Regarding the compounding ratio of the addition polymerizable compound in the photosensitive layer, a higher ratio is more sensitive and advantageous,
If the amount is too large, undesired phase separation occurs, problems in the production process due to the stickiness of the photosensitive layer (for example, production defects due to transfer of the photosensitive layer components and adhesion), and precipitation from the developing solution occur. Etc. may occur. From these viewpoints, the preferred compounding ratio is, in many cases, from 5 to 80% by weight, and preferably from 25 to 75% by weight, based on all components of the photosensitive layer. These may be used alone or in combination of two or more. In addition, the method of using the addition polymerizable compound can be arbitrarily selected from the viewpoints of the degree of polymerization inhibition with respect to oxygen, resolution, fogging property, refractive index change, surface tackiness, etc. Depending on the case, a layer configuration and a coating method such as undercoating and overcoating may be performed.

[Photopolymerization Initiator] Next, the photopolymerization initiator contained in the photopolymerizable photosensitive layer of the lithographic printing plate precursor according to the invention will be described. As the photopolymerization initiator contained in the photopolymerizable photosensitive layer of the lithographic printing plate precursor according to the invention, a known radical generator can be used. Examples of preferred radical generators include (a) aromatic ketones,
(B) an aromatic onium salt compound, (c) an organic peroxide,
(D) a hexaarylbiimidazole compound, (e) a ketoxime ester compound, (f) a borate compound,
(G) an azinium compound, (h) an active ester compound,
(I) a compound having a carbon-halogen bond, and (j) a metallocene compound.

(A) Examples of aromatic ketones include benzoin ether compounds described in JP-B-47-3981;
For example, the following are mentioned.

[0110]

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There are α-substituted benzoin compounds described in JP-B-47-22326, for example, the following.

[0112]

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The dialkoxybenzophenone compounds described in JP-B-60-26483, for example, include the following.

[0114]

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JP-B-60-26403, JP-A-62-206
The benzoin ether compounds described in JP 81345, for example, include the following.

[0116]

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JP-B-1-34242, US Pat. No. 43
Α-aminobenzophenone compounds described in EP 18791 and EP 0234561 A1, such as the following.

[0118]

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Examples of the p-di (dimethylaminobenzoyl) benzene compound described in JP-A-2-21152 include the following.

[0120]

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The thio-substituted aromatic ketone compounds described in JP-A-61-194062, for example, include the following.

[0122]

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

[0124]

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The acylphosphine compounds described in JP-B-2-9596, for example, include the following.

[0126]

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Further, mention may be made of thioxanthone compounds described in JP-B-63-61950 and coumarin compounds described in JP-B-59-42864.

Examples of (b) the aromatic onium salt which is another example of the radical generator include V, VI and VII of the periodic table.
Group elements, specifically N, P, As, Sb, Bi, O,
Includes aromatic onium salts of S, Se, Te or I. Examples of such aromatic onium salts include the compounds disclosed in JP-B-52-14277, JP-B-52-14278, and JP-B-52-14279. Specifically, the following can be mentioned.

[0129]

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[0130]

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[0131]

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The organic peroxide (c) which is another example of the radical generator includes almost all organic compounds having one or more oxygen-oxygen bonds in the molecule.
4,4'-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (t
-Amyl peroxycarbonyl) benzophenone, 3,
3'4,4'-tetra- (t-hexylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra-
(T-octylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (cumylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone And a peroxide ester such as di-t-butyl diperoxyisophthalate.

As another example of the radical generator (d) hexaarylbiimidazole compound, Japanese Patent Publication No.
-37,377 and JP-B-44-86516, for example, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (O-bromophenyl)-
4,4 ', 5,5'-tetraphenylbiimidazole,
2,2'-bis (o, p-dichlorophenyl) -4,
4 ', 5,5'-tetraphenylbiimidazole, 2,
2'-bis (o-chlorophenyl) -4,4 ', 5
5'-tetra (m-methoxyphenyl) biimidazole, 2,2'-bis (o, o'-dichlorophenyl)-
4,4 ', 5,5'-tetraphenylbiimidazole,
2,2'-bis (o-nitrophenyl) -4,4 ',
5,5'-tetraphenylbiimidazole, 2,2'-
Bis (o-methylphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-trifluorophenyl) -4,4', 5,5'-tetraphenylbi And imidazole.

Examples of (e) ketoxime ester compounds which are other examples of radical generators include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, and 3-propionyloxyiminobutane. -2
-One, 2-acetoxyiminopentan-3-one, 2
-Acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-p-toluenesulfonyloxyimiminobtan-2-one, 2-ethoxycarbonyloxyimino- 1-phenylpropan-1-one and the like.

As the borate compound (f) which is another example of the radical generator, a compound represented by the following formula (36) can be mentioned.

[0136]

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(Wherein R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ 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, wherein R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are two or more An annular structure may be formed. However,
At least one of R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ is a substituted or unsubstituted alkyl group. Z ⁺ represents an alkali metal thione or a fourth stage ammonium cation).

Specific examples of the compound represented by the general formula (36) include US Pat. Nos. 3,567,453 and 4,343,891 and European Patent 109,772.
And the compounds described in Nos. 109 and 773, for example, the following compounds.

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Another example of the radical generator (g), an azinium salt compound, is disclosed in JP-A-63-13834.
5, JP-A-63-142345, JP-A-63-14
No. 2346, JP-A-63-143537 and JP-B-46-43363. Examples of the radical generator include (h) active ester compounds which are other examples of radical generators. Examples thereof include imide sulfonate compounds described in JP-B-62-6223, and active sulfonates described in JP-B-63-14340 and JP-A-59-174831.

As another example of the radical generator (i) a compound having a carbon-halogen bond, Wakabayashi et al.,
Bull. Chem. Soc. Japan, 42, 2924 (1969)
Compounds described in British Patent No. 1388492, compounds described in JP-A-53-133428, compounds described in German Patent No. 3337024, FC
Schaefer et al., J. Org. Chem. 29, 1527 (196
The compounds described in 4), the compounds described in JP-A-62-58241, the compounds described in JP-A-5-281728, and the like are listed below.

[0142]

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[0143]

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Alternatively, (i) examples of compounds having a carbon-halogen bond include MPHutt and EF Elslage.
r and LM Herbel, Journal of Heterocyclic chem
istry ", Volume 7 (No. 3), pp. 511 et seq. (197
0), a group of compounds that can be easily synthesized by those skilled in the art according to the synthesis method described in German Patent No. 26
41100, a compound described in German Patent No. 3333450, a compound group described in German Patent No. 3021590, a compound group described in German Patent No. 3021599, and the like. There are the following.

[0145]

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[0146]

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[0147]

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Another example of the radical generator (j), a metallocene compound, is disclosed in JP-A-59-152396.
JP-A-61-151197, JP-A-63-414
No. 83, JP-A-63-41484, JP-A-2-249
Titanocene compounds described in JP-A No. 2-291, JP-A-3-27393, JP-A-3-12403, JP-A-6-41170, JP-A-1-304453
And an iron-allene complex compound described in JP-A-1-152109. Examples of the titanocene compound include di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,
3,4,5,6-pentafluorophenyl-1-yl (hereinafter also referred to as "T-1"), di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl- 1-yl, di-cyclopentadienyl-Ti-bis-
2,4,6-trifluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,6-difluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2, 4-difluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,
6-pentafluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, di-methylcyclopentadienyl-Ti- Bis-2,4-difluorophenyl-1
-Yl, bis (cyclopentadienyl) -bis (2,6
-Difluoro-3- (pyr-1-yl) phenyl) titanium and the like.

More preferred examples of the radical generator contained in the photopolymerizable photosensitive layer of the lithographic printing plate precursor according to the invention include the aforementioned (i) the compound having a carbon-halogen bond,
(J) Metallocene compounds can be mentioned.

The radical generator contained in the photopolymerizable photosensitive layer of the lithographic printing plate precursor according to the invention is preferably used alone or in combination of two or more. In addition, the radical generator may be further subjected to various chemical modifications for improving the characteristics of the photosensitive layer of the lithographic printing plate precursor according to the invention. For example, bonding with a sensitizing dye described below or the above-described addition-polymerizable unsaturated compound or other radical generating part, introduction of a hydrophilic site, improvement of compatibility, introduction of a substituent for suppressing crystal precipitation, and improvement of adhesion. For example, a method of introducing a substituent, polymerizing, or the like can be used.

The use of these radical generators can be set as appropriate according to the performance design of the lithographic printing plate precursor. For example, by using two or more kinds, the compatibility of the lithographic printing plate precursor of the invention with the photosensitive layer can be enhanced. It is advantageous in terms of photosensitivity that the use amount of the radical generator is usually large, and it is 0.5 to 100 parts by weight of the photosensitive layer component.
Sufficient photosensitivity can be obtained when used in an amount of from 80 to 80 parts by weight, preferably from 1 to 50 parts by weight.

Further, a sensitizing dye can be added to the photopolymerizable photosensitive layer of the lithographic printing plate precursor according to the invention in combination with a photopolymerization initiator. At present, a visible light laser having a wavelength of 400 to 700 nm is excellent as a scanning exposure light source for plate making, and it is preferable to add a visible light sensitizing dye. Preferred visible light sensitizing dyes include a) a cyanine dye, b) a merocyanine dye, c) a xanthene dye, d) a ketocoumarin dye, and e) a benzopyran dye.

A) Preferable examples of the cyanine dye include those having the following structure described in JP-A-8-234428, but are not limited thereto.

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(Wherein, Z ¹ and Z ² may be the same or different and represent a group of nonmetallic atoms necessary for forming a benzimidazole or naphthoimidazole ring. R ¹ ,
R ² , R ³ and R ⁴ each represent an optionally substituted alkyl group. X ⁻ represents a counter anion, and n is 0 or 1.
It is. )

Table 1 below shows specific examples of cyanine dyes.

[0157]

[Table 1]

Preferred examples of b) merocyanine dyes, which are other examples of visible light sensitizing dyes, are described in JP-A-8-234.
429, JP-A-8-220758 and JP-A-8-22
No. 0757, which has the following structure, but is not limited thereto.

[0159]

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(Wherein, Z ¹ and Z ² each represent a nonmetallic atom group necessary for forming a 5-membered and / or 6-membered nitrogen-containing heterocyclic ring usually used in cyanine dyes. R ¹ , R ²
Each represents an alkyl group. Q ¹ and Q ² combine to form a 4-thiazolidinone ring, a 5-thiazolidinone ring, a 4-imidazolidinone ring, a 4-oxazolidinone ring, a 5-oxazolidinone ring, a 5-imidazolidinone ring or a 4-dithiolanone ring. Represents the group of atoms required to perform m represents 1 or 2. i and h are 0 or 1 respectively
Represents l represents 1 or 2. j and k are 0,
Represents 1, 2, or 3. X ^- represents a counter anion. )

[0161]

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(Wherein R ¹ and R ² are each independently a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent. A represents an alkynyl group, an alkoxycarbonyl group, an aryl group or an aralkyl group which may have a substituent, and A represents an oxygen atom,
Represents a sulfur atom, a selenium atom, a tellurium atom, an alkyl or aryl substituted nitrogen atom or a dialkyl substituted carbon atom. X represents a nonmetallic atom group necessary to form a nitrogen-containing 5-membered heterocyclic ring. Y represents a substituted phenyl group, a polynuclear aromatic ring which may have a substituent, or a heteroaromatic ring which may have a substituent. Z is a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, an aralkyl group, an alkoxy group, an alkylthio group, an arylthio group, a substituted amino group, an acyl group, or an alkoxycarbonyl group And may combine with Y to form a ring. )

[0163]

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(Where A = is optionally substituted 2 (3
H) - Chiazoririden represents a group or a 2-thiazolidinylidene group, -X- is -O -, - S -, - NR 2 - or -CONR ³ - ^{represents, R 1, R 2, R} 3 are each And independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkenyl group, or an optionally substituted alkynyl group, and は E represents an optionally substituted 1 , 3-dihydro-1-oxo-2H-indene-2-ylidene group. Hereinafter, specific examples of the merocyanine dye will be described.

[0165]

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[0166]

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Preferred examples of the c) xanthene dye, which is another example of the visible light sensitizing dye, include rhodamine B, rhodamine 6G, ethyl eosin, alcohol-soluble eosin, pinilone Y, and pinilone B.
Preferable examples of d) ketocoumarin dyes, which are other examples of visible light sensitizing dyes, include those having the following structure described in JP-A-63-221110, but are not limited thereto.

[0168]

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(Wherein R ¹ , R ² and R ³ each represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, and R ³ and R ⁴ each represent an alkyl group, at least one of which has 4 carbon atoms. Represents up to 16 alkyl groups,
R ⁶ represents a hydrogen atom, an alkyl group, an alkoxy group, an acyl group, a cyano group, a carboxyl group, or a group of an ester derivative or an amide derivative thereof, and R ⁷ represents a heterocyclic residue having 3 to 17 carbon atoms in total. It represents a group -CO-R ^8, R ² and R ^3, R ⁴ and R ⁵ may be bonded to each other to form a ring. Here, R ⁸ is a group shown below.

[0170]

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The following are specific examples of ketocoumarin dyes.

[0172]

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Preferred examples of e) a benzopyran-based dye which is another example of the visible light sensitizing dye include JP-A-8-334.
No. 897 having the following structure,
It is not limited to this.

[0174]

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[0175] (wherein, R ¹ to R ⁴ 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. Further, R ¹ ~
R ⁴ may form a ring composed of a non-metallic atom together with the carbon atoms to which they can be respectively bonded. R ⁵ 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. R ⁶ is a group represented by R ⁵ or —ZR ⁵ , and Z represents a carbonyl group, a sulfonyl group, a sulfinyl group, or an arylenedicarbonyl group. R ⁵ and R ⁶ may together form a ring composed of non-metallic atoms.
A represents O, S, NH or a nitrogen atom having a substituent. B is an oxygen atom or the following group

[0176]

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And G ₁ and G ₂ may be the same or different and each represents 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. Group, arylsulfonyl group or fluorosulfonyl group. However, G ₁ and G ₂ are not simultaneously hydrogen atoms. G ₁ and G ₂ may form a ring composed of a non-metal atom together with a carbon atom. Examples of benzopyran-based dyes are shown below.

[0178]

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[0179]

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Preferred examples of the sensitizing dye include:
The above-mentioned b) merocyanine dyes and e) benzopyran dyes are preferred. The sensitizing dyes are also suitably used alone or in combination of two or more. As for the sensitizing dye,
Further, various chemical modifications for improving the characteristics of the photosensitive layer of the lithographic printing plate precursor according to the invention can be performed.
For example, by bonding a sensitizing dye and the above-described addition-polymerizable compound structure (for example, an acryloyl group or a methacryloyl group) by a method such as a covalent bond, an ionic bond, or a hydrogen bond, the strength of the exposed film can be increased. In addition, unnecessary precipitation of the dye from the film after exposure can be suppressed. In addition, the sensitizing dye and the above-described radical generator and other radical generating parts (for example, reductively decomposable sites such as alkyl halide, onium, peroxide, biimidazole, onium, biimidazole, etc., borate, amine, trimethylsilyl) By binding to oxidatively decomposable sites such as methyl, carboxymethyl, carbonyl, and imine), the photosensitivity can be remarkably increased, particularly in the case where the concentration of the photopolymerization initiation system is low. Further, for the purpose of enhancing the suitability of processing the photosensitive layer of the lithographic printing plate precursor according to the present invention in an (alkali) aqueous developer, a hydrophilic site (carboxyl group and its ester, sulfonic acid) It is effective to introduce a group and its ester, an acid group such as an ethylene oxide group or a polar group). Particularly, the ester-type hydrophilic group has a relatively hydrophobic structure in the photosensitive layer and thus has excellent compatibility, and in a developing solution, generates an acid group by hydrolysis to increase the hydrophilicity. Have. In addition, for example, a substituent can be appropriately introduced for improving compatibility in the photosensitive layer and suppressing crystal precipitation. For example, in certain types of photosensitive systems, unsaturated bonds such as aryl groups and allyl groups may be very effective in improving compatibility. By introducing an obstacle, crystal precipitation can be significantly suppressed. Further, by introducing a phosphonic acid group, an epoxy group, a trialkoxysilyl group, or the like, it is possible to improve the adhesion to inorganic substances such as metals and metal oxides. In addition, a method such as polymerization of a sensitizing dye can be used depending on the purpose.

The method of using these sensitizing dyes can be arbitrarily set in accordance with the performance design of the lithographic printing plate precursor as in the case of the aforementioned radical generator. For example, by using two or more sensitizing dyes in combination, the compatibility with the photosensitive layer can be increased. In selecting a sensitizing dye, the molar extinction coefficient at the emission wavelength of the light source used is an important factor in addition to the photosensitivity. By using a dye having a large molar extinction coefficient, the amount of the dye added can be relatively small, which is economical and advantageous from the viewpoint of the physical properties of the photosensitive layer. Since the photosensitivity and resolution of the photosensitive layer and the physical properties of the exposed film are greatly affected by the absorbance at the wavelength of the light source, the amount of the sensitizing dye to be added is appropriately selected in consideration of these factors. For example, the sensitivity is reduced in a low region where the absorbance is 0.1 or less. Also, the resolution becomes low due to the influence of halation. However, for the purpose of curing a thick film having a thickness of, for example, 5 μm or more, such a low absorbance may increase the degree of curing. The absorbance is 3
In the high region as described above, most of the light is absorbed on the surface of the photosensitive layer, and curing inside is more hindered.For example, when used as a printing plate, the film strength and the substrate adhesion are considered to be insufficient. Become. When used as a lithographic printing plate precursor having a relatively thin film thickness, the amount of the sensitizing dye to be added is such that the absorbance of the photosensitive layer is in the range of 0.1 to 1.5, preferably 0.2 to 1.5.
It is preferable to set the value in the range of 5 to 1. When used as a lithographic printing plate precursor, it is usually used in an amount of 0.05 to 30 parts by weight, preferably 0.1 to 20 parts by weight, more preferably 0.2 to 20 parts by weight, based on 100 parts by weight of the photosensitive layer component. The range is from 10 to 10 parts by weight.

Further, a coinitiator can be added to the photopolymerizable photosensitive layer of the lithographic printing plate precursor according to the invention for the purpose of improving sensitivity. For example, amine compounds, thiol compounds,
Oxime ether compounds and the like can be mentioned. Of these, preferred examples of the oxime ether compound include compounds having the following structure described in JP-A-10-237118, but are not limited thereto.

[0183]

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(Wherein, R ^{1 to} R ⁴ represent an alkyl group or an aryl group, and Ar represents an aryl group. Further, R ¹ and R ² or R ³ and R ⁴ are bonded to each other to form a ring. You may.
Z represents a hydrocarbon-containing linking group which may have a divalent substituent. Y represents a divalent linking group or a single bond containing at least one of the groups shown below.

[0185]

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Here, R ⁵ is a hydrogen atom, a hydrocarbon group which may have a substituent or may contain an unsaturated bond,
Represents a carbonyl group or a sulfonyl group. Also, R ⁵ ~
R ⁸ is the same or different and represents a hydrocarbon group which may have a substituent or may contain an unsaturated bond.
T ⁻ represents a monovalent anion or a monovalent sulfonate anion comprising a logen atom. X is a group having an addition-polymerizable group represented by the following formula [Ia].

[0187]

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And r ^{1 to} r ³ are the same or different and represent a hydrogen atom, a methyl group, an ethyl group, a phenyl group, a halogen atom, a cyano group or —C (＝ O) —OR ⁹ .
n represents 0 or 1. However, when n is 0, all of r ^{1 to} r ³ do not become hydrogen atoms. r ⁴ and r ⁵ are the same or different and represent a hydrogen atom, a methyl group, an ethyl group or a phenyl group. R ⁹ represents an alkyl group or an aryl group. Table 2 below shows examples of oxime ether compounds.

[0189]

[Table 2]

Particularly preferred as co-initiators are the oxime ether compounds described above. As with the above sensitizing dyes, these co-sensitizers can be further subjected to various chemical modifications to improve the characteristics of the photosensitive layer. For example, binding with sensitizing dyes, radical generators, addition-polymerizable unsaturated compounds and other radical-generating parts, introduction of hydrophilic sites, improvement of compatibility, introduction of substituents for suppressing crystal precipitation, and improvement of adhesion Methods such as substituent introduction and polymerization can be used. These coinitiators can be used alone or in combination of two or more. The amount is suitably in the range of 0.05 to 100 parts by weight, preferably 1 to 80 parts by weight, more preferably 3 to 50 parts by weight, per 100 parts by weight of the compound having an ethylenically unsaturated double bond.

In the photopolymerizable photosensitive layer of the lithographic printing plate precursor according to the invention, the urethane binder, the addition polymerizable compound,
In addition to the basic components of the photopolymerization initiator, a small amount of a thermal polymerization inhibitor is added during the production or storage of the photosensitive layer component composition to prevent unnecessary thermal polymerization of the addition polymerizable compound. Is desirable. Suitable thermal polymerization inhibitors include haloquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-tert-butylphenol) ), 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxylamine cerium salt, N
-Nitrosophenylhydroxylamine aluminum salt and the like. The addition amount of the thermal polymerization inhibitor is preferably from about 0.01% to about 5% based on the weight of the whole composition. If necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to prevent polymerization inhibition by oxygen, and may be unevenly distributed on the surface of the photosensitive layer in a drying process after coating. . The addition amount of the higher fatty acid derivative is preferably about 0.5% to about 10% of the whole composition.

Further, a coloring agent may be added for the purpose of coloring the photopolymerizable photosensitive layer of the lithographic printing plate precursor according to the invention.
Examples of the coloring agent include phthalocyanine pigments (CI
Pigment Blue 15: 3, 15: 4, 15: 6), azo pigments, pigments such as carbon black and titanium oxide, ethyl violet, crystal violet, azo dyes, anthraquinone dyes, and cyanine dyes. The amount of dye and pigment added is preferably about 0.5% to about 20% of the total composition.
In addition, additives such as inorganic fillers and plasticizers such as dioctyl phthalate, dimethyl phthalate and tricresyl phosphate may be added to improve the physical properties of the cured film. The amount of these additives is preferably 10% or less of the total composition of the photosensitive layer components.

In the lithographic printing plate precursor of the present invention, when the photopolymerizable photosensitive layer is coated on a support described below, the photosensitive layer component composition is dissolved in various organic solvents and used. You. As the solvent used here, 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, methyl lactic acid Ethyl and the like. These solvents can be used alone or as a mixture. The appropriate concentration of the solid content in the coating solution is 1 to 50% by weight.

A surfactant can be added to the photopolymerizable photosensitive layer of the lithographic printing plate precursor according to the invention in order to improve the coated surface quality. The coating amount of the photopolymerizable photosensitive layer is in the range of about 0.1 g / m ² ~ about 10 g / m ² in weight after drying is suitable. More preferably, it is 0.3 to 5 g / m ² . More preferably, it is 0.5 to 3 g / m ² .

[Aluminum Support] The aluminum support used in the lithographic printing plate precursor according to the present invention is a metal mainly containing dimensionally stable aluminum.
It is made of aluminum or aluminum alloy. In addition to a pure aluminum plate, it is selected from an alloy plate containing aluminum as a main component and containing a trace amount of a different element, or a plastic film or paper on which aluminum (alloy) is laminated or evaporated. Further, a composite sheet in which an aluminum sheet is bonded to a polyethylene terephthalate film as described in JP-B-48-18327 may be used.

In the following description, the above-mentioned substrates made of aluminum or aluminum alloy are collectively used as aluminum substrates. The foreign elements contained in the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel and titanium, and the content of the foreign elements in the alloy is 10% by weight or less. In the present invention, a pure aluminum plate is preferable, but completely pure aluminum is difficult to produce due to refining technology, and therefore may contain a slightly different element. As described above, the composition of the aluminum plate applied to the present invention is not specified, and any of conventionally known and used materials such as JIS A 1050 and JISA 110 can be used.
0, JIS A 3103, JIS A 3005, and the like can be used as appropriate.

The thickness of the aluminum substrate used in the present invention is about 0.1 mm to 0.6 mm. This thickness can be appropriately changed according to the size of the printing press, the size of the printing plate, and the user's request.

The aluminum substrate used in the present invention particularly preferably has the following physical properties. Cutoff 0.8, scanning speed 0.3 mm / sec using Surfcom 575 manufactured by Tokyo Seimitsu Co., Ltd.
c. When the roughness parameter according to JIS was measured on the surface of the support when measured at a measurement length of 3 mm under the condition of a stylus tip total of 2 μm R, the center line average roughness Ra was 0.20 to 0.20.
0.70 μm, 10-point average roughness Rtm is 1.0 to 5.0
μm, square root roughness RMS or Rq is 0.2-2.0μ
m, average peak interval Sm is 20 to 80 μm, reference level ± 0.
The peak count Pc at 5 μm is 10 to 70, the average slope gradient Δa is 5 to 12 deg, and the initial wear load ratio Mr ₁ is 1
When the surface of the support is polished and the crystal structure in the vicinity of the surface of the aluminum support is observed with an optical microscope, and the surface recrystallized grain width is determined as an average value of 100 crystal grains, it is 3 to 15%. 60 μm, and with respect to the density on the surface of the support, the lightness L ^* measured by a color difference meter was 40 to 8
0, the support surface concentration by Macbeth densitometer is 0.15
Those having a range of 0.35.

(Silicate Treatment) The aluminum substrate is appropriately subjected to a graining treatment, which will be described later, or the like, and then the surface of the substrate is subjected to a hydrophilic treatment with silicate. The hydrophilization treatment with silicate in the present invention is the formation of a silicate film, and the silicate film has a Si element content of 0.5 to
40 mg / m ^2, more preferably 1 to 30 mg / m ² formed. The coating amount can be measured by fluorescent X-ray analysis,
Elemental amounts can be measured. The above hydrophilization treatment,
For example, as described in JP-B-47-5125, an aluminum plate which is anodized and then immersed in an aqueous solution of an alkali metal silicate is preferably used. U.S. Pat. Nos. 2,714,066 and 3,
No. 181,461, 3,280,734 and 3,902,734, an alkali metal silicate (for example, sodium silicate aqueous solution) method can be applied. According to this method, the alkali metal silicate is 1 to 30% by weight, preferably 2 to 15% by weight.
In an aqueous solution having a pH of 10 to 13 at 25 ° C., an aluminum substrate on which an anodized film is formed
Immerse for 0.5 to 120 seconds at 5 to 80 ° C.

As the alkali metal silicate used in the present invention, sodium silicate, potassium silicate, lithium silicate and the like are used. Hydroxides used to increase the pH of the aqueous alkali metal silicate solution include sodium hydroxide, potassium hydroxide and lithium hydroxide.
In addition, alkaline earth metal salts or IV
A group B metal salt may be blended. Alkaline earth metal salts include nitrates such as calcium nitrate, strontium nitrate, magnesium nitrate and barium nitrate, and water-soluble salts such as sulfates, hydrochlorides, phosphates, acetates, oxalates and borates. No.

Group IVB metal salts include titanium tetrachloride, titanium trichloride, potassium titanium fluoride, potassium titanium oxalate, titanium sulfate, titanium tetraiodide, zirconium chloride, zirconium dioxide, zirconium oxychloride, zirconium tetrachloride, and the like. Can be mentioned. Alkaline earth metal salts or Group IVB metal salts can be used alone or in combination of two or more. The preferred range of these metal salts is 0.01 to 10% by weight, and the more preferred range is 0.05 to 5.0% by weight.

Further, silicate electrodeposition as described in US Pat. No. 3,658,662 is also effective. Further, Japanese Patent Publication No. 46-27481 and Japanese Patent Application Laid-Open No. 52-5860.
No. 2, JP-A-52-30503, and a surface treatment obtained by combining the anodizing treatment and the sodium silicate treatment with a support provided with electrolytic grains are also useful.

(Acid treatment) The aluminum substrate subjected to the silicate treatment as described above is further treated with an acidic solution. The acid used at this time is hydrochloric acid, sulfuric acid,
Nitric acid, phosphoric acid, oxalic acid, chromic acid, sulfamic acid,
Benzenesulfonic acid and the like may be mentioned, but two or more of these may be used in combination. As the acid treatment liquid used in the present invention, an acidic aqueous solution having a pH of 0 to 6 is desirable. If the pH of the acid treatment liquid is lower than 0, handling is dangerous and production suitability is poor, and if the pH is higher than 6, a sufficient effect of improving the adhesion cannot be obtained. As an acid treatment condition at this time, for example, it is appropriate to carry out by immersing at a temperature of 10 to 80 ° C. for 1 to 300 seconds.

The reason why the adhesion between the support and the photopolymerizable photosensitive layer is improved by the acid treatment is not clear, but is considered as follows. It has been found from the results of X-ray fluorescence analysis and ESCA analysis that the acid treatment reduces the silicate adsorption amount by 5 to 30% and the metal ions such as Na and Ca present in a small amount in the silicate film. One more
After treatment with specified Na ₂ CO ₃ at 25 ° C. for 10 seconds, washing with distilled water and drying, the amount of Na was measured by ESCA. By this treatment, the SiOH of the silicate film becomes SiONa, and the amount of SiOH of the silicate film can be estimated. According to this measurement, the amount of Na was increased by the acid treatment. That is, it is considered that the acid treatment increased the SiOH groups on the silicate surface.

Further, when the aluminum support is left for 12 hours in a 0.5% aqueous solution of the crystal dye violet, which is a cationic dye, the support which has been subjected to the acid treatment has a significantly lower dyeing concentration than the support which has not been subjected to the acid treatment. I understand.
This is presumably because the acid treatment reduced the negative charge on the surface of the support, which made it difficult to adsorb crystal violet, which is a cationic dye. In other words, the acid treatment reduces the amount of metal ions in Na, Ca, etc. present in a small amount on the silicate surface and increases the SiOH groups. Therefore, when an adhesive layer described below is applied, the number of chemical bonding sites between the silicate layer and the adhesive layer increases. As a result, it is considered that the adhesion between the aluminum support and the photopolymerizable photosensitive layer was improved.

(Adhesion Layer) The aluminum substrate thus treated with silicate and acid is further provided with a silicone having a functional group capable of causing an addition reaction by a radical (hereinafter referred to as an addition-reactive functional group) on its surface. An adhesive layer containing the compound is applied. The coating of the layer containing the silicone compound having an addition-reactive functional group is preferably performed by a method using an organic silicone compound as a raw material. Specifically, when the addition-reactive functional group is represented by R ¹⁸ , the following general formula (37):

R ¹⁸ Si (OR ¹⁹ ) ₃ General formula (37)

By treating an aluminum substrate with an organosilicone compound represented by the formula (-OR ¹⁹ is a hydrolyzable alkoxy group or -OCOCH ₃ group), metal and metal oxide on the surface of the substrate are treated. Reacts with a substance, a hydroxide, an —OH group, or a silanol group formed by chemical conversion treatment of the substrate to form a covalent bond with the substrate surface, and has the following general formula (38):

(R ²⁰ O) ₂ (R ¹⁸ ) Si—General formula (38)

The functional group represented by the formula (1) may be bonded (or implanted) to the substrate surface. In the formula, R ²⁰ represents a same or different alkyl group or a hydrogen atom as R ¹⁹ , or a bond to another adjacent Si atom. In the above, the following general formula (39) or (40) wherein two or more addition-reactive functional groups (R ¹⁸ ) are bonded to a central Si atom:

(R ¹⁸ ) ₂ Si (OR ¹⁹ ) ₂ General Formula (39) (R ¹⁸ ) ₃ SiOR ₁₉ General Formula (40)

An organic silicone compound represented by the following formula can also be used. Further, the addition-reactive functional group (R ¹⁸ )
When the functional group is bonded to the central Si atom via O-,

(R ¹⁸ ) ₄ Si General formula (41)

The organic silicone compound represented by the formula (1) can also be used. The organic silicone compound (37) has at least one of the four R ¹⁸ bonded to the central Si atom.
It is applied to the aluminum substrate when the individual remains without being hydrolyzed. When applying the organosilicone compound (37) on an aluminum substrate, it may be used alone, or may be used after being diluted with a suitable solvent.
Water and / or a catalyst can be added to bind the organosilicone compound (37) more firmly on the aluminum substrate. As the solvent, alcohols such as methanol, ethanol, propanol, isopropanol, ethylene glycol and hexylene glycol are preferable, and as a catalyst, acids such as hydrochloric acid, acetic acid, phosphoric acid, and sulfuric acid;
Alternatively, a base such as ammonia or tetramethylammonium hydroxide can be used.

[0215] The amount of addition-reactive functional groups on the aluminum substrate varies depending on the type of addition-reactive functional group to be bonded, ² per generally 0.01 to 1000 pieces 10 nm, preferably from 0.05 to 200, still Preferably 0.1 to
It is appropriate to use 50. Sufficient light adhesive strength and addition-reactive functional group content is less than ² per 0.01 pieces 10nm difficult to obtain. By applying the organosilicone compound (37) thickly, the amount of the addition-reactive functional group per 10 nm ² can be substantially increased. Is 10 nm ²
Since there are at most 10 pieces, even if it is applied too thickly, it is useless. In order that the amount of the addition-reactive functional group is excessive and the hydrophilicity of the non-image area when used as a PS plate is not insufficient, 10n
It is preferable that the amount of the addition-reactive functional group per m ^{2 be} 1000 or less.

Therefore, when the addition-reactive functional group is bonded (planted) to the aluminum substrate surface using the organic silicone compound, the type and amount of the solvent for diluting the organic silicone compound and the hydrolysis on the substrate surface are reduced. The amount of water to be added (if added), the type and amount of catalyst for promoting hydrolysis on the substrate surface (if added), the method of applying the organic silicone compound solution on the substrate, and the method after application to the substrate It is necessary to variously change process parameters such as a drying atmosphere, a drying temperature, and a drying time, and to control the amount of the addition-reactive functional group held on the substrate surface to be within the above range. The amount of the addition-reactive functional group retained on the aluminum substrate surface is measured by an appropriate method such as a fluorescent X-ray analysis method or an infrared absorption method on the substrate surface after the treatment, and the amount of the Si atom on the surface is determined. It can be determined by performing quantification, quantification of the amount of carbon-carbon multiple bonds, and the like.

As described above, an anodized film and a silicate film are formed on an aluminum substrate, and an addition-reactive functional group is bonded to the surface thereof, thereby completing the support of the present invention.
However, when a PS plate is formed using this support (addition reactive support), simply treating the aluminum substrate using only the organosilicone compound of the general formula (37) may cause printing stains. is there. That is, a photopolymerizable photosensitive composition is coated on a support having an addition-reactive functional group attached thereon to form a photosensitive layer, and imagewise exposure is performed on this to cause image-wise interfacial light adhesion, By removing the unexposed portion with the developing solution, a photopolymerized adhesion film remains on the support according to the light pattern. Then, when ink and water are applied to the ink, the ink adheres to the imagewise exposed portion that has been photopolymerized and adhered, and the water adheres to the unexposed portion to form a printing plate, but when the organic silicone compound is used alone, In some cases, excessive organic functional groups may be present in unexposed areas to which water is to adhere, and ink may also adhere in addition to water, which may be observed as stains on printed matter.

Therefore, in order to prevent this printing stain, it is preferable to fix a large number of OH groups in addition to the addition-reactive functional group (R ¹⁸ ) on the surface of the aluminum substrate to enhance the hydrophilicity. Preferably, the binding of addition-reactive functional group to the aluminum substrate surface, the general formula (37): R ¹⁸ Si
(OR ¹⁹ ) _{3 In} addition to the organic silicone compound represented by ₃ ,
General formula (42): Si (OR ²¹ ) ₄ (wherein —OR ²¹ is a hydrolyzable alkoxy group, an alkoxyalkoxy group,
It is an aryloxy group or an —OCOCH ₃ group, and R ²¹ may be the same as or different from R ¹⁹ . The organic silicone compound represented by the formula (38) is used in combination with the reaction site represented by the general formula (38) on the substrate surface.
The following general formula (43):

(R ²² O) ₂ (OH) Si—General formula (43)

It is preferable to bind the hydrophilic site represented by Here, in the formula, R ²² represents an alkyl group, a hydrogen atom, or a bond to another adjacent Si atom, and it is most preferable that R ²² be a hydrogen atom from the viewpoint of hydrophilicity.
When R ²² is other than a hydrogen atom, the surface can be washed with an alkali solution to increase the hydrophilicity, if necessary.

The mixing ratio of the organic silicone compound of the general formula (37) and the organic silicone compound of the general formula (42) depends on the properties of the support, and the efficiency of bonding (planting) each of them to the surface of the support is determined. Because of the variation, a suitable range cannot be determined. However, specifically, the support was treated by changing the ratio of the two in various ways, and the photoadhesiveness based on the addition-reactive functional group R ¹⁸ and the general formula (4)
The condition for achieving compatibility with the hydrophilicity derived from the partial structure shown in 3) will be experimentally determined and used. In any case, the density of the addition-reactive functional group should be within the above range. Specifically, the mixing molar ratio of the organic silicone compound (42) to the organic silicone compound (37) is appropriately 0.05 to 500, preferably 0.2 to 200, and more preferably 1 to 100. . Further, within this range, as the amount of the hydrophilic group derived from the organosilicone compound of the general formula (42) increases, the hydrophilicity of the non-image portion increases. However, even when the density of the hydrophilic group is low, the density of the hydrophilic group can be improved by hydrophilizing the addition reactive functional group.

The bonding of the addition-reactive functional group to the aluminum substrate surface can be roughly classified, in addition to the above-mentioned method (hereinafter, referred to as SC method) using an organic silicone compound as it is, using an organic silicone compound. A method comprising using an organic-inorganic composite in which an addition-reactive functional group is fixed to an inorganic polymer containing a -Si-O-Si- bond obtained by hydrolysis and polycondensation (hereinafter referred to as SG). Called the law). When this organic-inorganic composite is applied to an aluminum substrate and dried, the inorganic polymer portion adheres to the substrate, and the addition-reactive functional group remains on the substrate surface as it is.

In the case of the SC method, the bonding position of the addition-reactive functional group on the surface of the aluminum substrate tends to be a position having a specific property on the surface of the substrate, and it may be difficult to uniformly distribute the functional group on the surface of the substrate. is there. That is, a covalent bond with the Si atom is formed only at a specific acid point or base point, and the distribution of the addition-reactive functional group is likely to be controlled by the distribution of acid points or base points on the aluminum substrate surface. Therefore, unevenness may occur in the optical adhesive strength and the non-image area hydrophilicity. In such situations, it is advantageous to follow the SG method.

In detail, in addition to the SC method and the SG method, in addition to the intermediate method, for example, a part or all of OR ¹⁹ in the organic silicone compound of the general formula (37): R ¹⁸ Si (OR ¹⁹ ) ₃ A treatment using an organic silicone compound in a form of two or three molecules bonded by hydrolysis as a starting material is also possible. According to the method of bonding an addition-reactive functional group by the SG method, the organosilicone compound of the general formula (37) is optionally mixed with the organosilicone compound of the general formula (42) at a desired mixing ratio. In the presence of a catalyst, if necessary, the addition-reactive functional group R ¹⁸ is -OR
Hydrolysis at ¹⁹ and -OR ²¹ and polycondensation reaction to form a liquid composition containing an inorganic polymer in which the central Si atom is connected by -Si-O-Si- bonds, Coating and optional drying binds the addition-reactive functional groups on the substrate.

When the SG method is used, the distribution of the addition-reactive functional groups bonded and fixed on the aluminum substrate surface is hardly influenced by the distribution of chemical properties such as acid sites and base sites on the substrate surface. When an organic silicone compound (42) is used as a starting material in addition to the organic silicone compound (37), the addition-reactive functional group site represented by the general formula (38) and the general formula (43) are used. Since the relative ratio to the hydrophilic site is substantially determined by the charge ratio of the organosilicone compound (37) and the compound (42), there is an advantage that the route for determining the prescription for obtaining the optimum surface is more orderly than the SC method.

Specific examples of the organic silicone compound represented by the above general formula (37) used in the present invention include the following.

[0227] _{CH 2 = CH-Si (OCOCH} 3) 3, CH 2 = CH-Si (OC 2 H 5) 3, CH 2 = CH-Si (OCH 3) 3, CH 2 = CHCH 2 -Si (OC _{2 H 5) 3, CH 2} = CHCH 2 NH (CH 2) 3 -Si (OCH 3) 3, CH 2 = CHCOO- (CH 2) 3 -Si (OCH 3) 3, CH 2 = CHCOO- (CH _{2) 3 -Si (OC 2 H} 5) 3, CH 2 = C (CH 3) COO- (CH 2) 3 -Si (OCH 3) 3, CH 2 = C (CH 3) COO- (CH 2) ₃ -Si (OC
_{2 H 5) 3, CH 2} = C (CH 3) COO- (CH 2) 4 -Si (OCH 3) 3, CH 2 = C (CH 3) COO- (CH 2) 5 -Si (OCH 3) _{3, CH 2 = CHCOO- (CH} 2) 4 -Si (OCH 3) 3, (CH 2 = C (CH 3) COO- (CH 2) 3) 2 -Si (OCH
_{3) 2, CH 2 = C} (CH = CH 2) -Si (OCH 3) 3, CH 2 = CH-SO 2 NH- (CH 2) 3 -Si (OCH 3) 3, CH 2 = CH-ph _{-O-Si (OCH 3) 3} , CH 2 = CH-ph-CONH- (CH 2) 3 -Si (OCH
_{3) 3, CH 2 = CH} -ph-CH 2 NH- (CH 2) 3 -Si (OC
_{H 3) 3, ph: HC≡C} -Si (OC 2 H 5 showing a benzene _{ring) 3, CH 3 C≡C-Si} (OC 2 H 5) 3,

[0228]

Embedded image

CH ₂ ＣＨCHCH ₂ O—Si (OCH ₃ ) ₃ , (CH ₂ ＣＨCHCH ₂ O) ₄ Si, HO—CH ₂ —C≡C—Si (OC ₂ H ₅ ) ₃ , CH ₃ CH ₂ CO—C≡C—Si (OC ₂ H ₅ ) ₃ , CH ₂ ＣＨCHS— (CH ₂ ) ₃ —Si (OCH ₃ ) ₃ , CH ₂ ＣＨCHCH ₂ O— (CH ₂ ) ₂ —SCH ₂ —Si (OCH
_{3) 3, CH 2 = CHCH} 2 S- (CH 2) 3 -S-Si (OCH 3) 3, (CH 3) 3 CCO-C≡C-Si (OC 2 H 5) 3, (CH 2 = CH) ₂ N— (CH ₂ ) ₂ —SCH ₂ —Si (OC
_{H 3) 3, CH 3 COCH} = C (CH 3) -O-Si (OCH 3) 3.

Specific examples of the organic silicone compound represented by the general formula (42) include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetra (n-propoxy) silane, and tetra (n-butoxy) silane. , Tetrakis (2-ethylbutoxy) silane, tetrakis (2-ethylhexyloxy) silane, tetrakis (2-methoxyethoxy) silane, tetraphenoxysilane, tetraacetoxysilane, etc., among which tetraethoxysilane is preferable.

The type of solvent, the method of application to the substrate, the drying method, and the like are the same in both cases of using the SC method and the SG method to bond the addition-reactive functional group to the aluminum substrate surface. In the case of the method, it is necessary to prepare an inorganic polymer composition having an addition-reactive functional group in advance. Preferred examples are shown below. The general formula (3)
Solvents that can be used to polycondensate the organosilicone compounds (37) and (42) represented by 7) and (42) together with hydrolysis to obtain a composition suitable for the SG method include methanol, ethanol, propanol, and isopropanol. And alcohols such as ethylene glycol and hexylene glycol.

The amount of the solvent to be used is generally 0.2 to 500 times, preferably 0.5 to 100 times, more preferably 1 to 100 times, based on the total weight of the organic silicone compounds (37) and (42) used. 20 times. If the used amount is less than 0.2 times, the reaction solution is apt to gel over time and becomes unstable, which is not preferable. If it is more than 500 times, the reaction takes several days, which is not preferable. The amount of water added to hydrolyze the organic silicone compound is generally 0.1 to 1000 mol, preferably 0.5 to 200 mol, more preferably 1.5 to 10 mol per mol of the organic silicone compound.
0 mol. When the amount of water is less than 0.1 mol per 1 mol of the organic silicone compound, the progress of the hydrolysis and the subsequent polycondensation reaction becomes very slow, and it takes several days before stable surface treatment becomes possible. But not preferred. On the other hand, when the amount of water is more than 1000 mol per 1 mol of the organic silicone compound, when the resulting composition is applied to a metal surface, poor adhesion occurs, and the composition has poor stability over time and gels immediately. In many cases, it becomes difficult to perform the coating operation stably.

The reaction temperature for preparing a composition suitable for the SG method is usually from room temperature to about 100 ° C., but depending on the type of the catalyst described below, a temperature below room temperature or above 100 ° C. may be used. it can. It is also possible to carry out the reaction at a temperature higher than the boiling point of the solvent, and if necessary, a reflux condenser may be provided in the reactor. Examples of the catalyst used as necessary include acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, malic acid, and oxalic acid, and bases such as ammonia, tetramethylammonium hydroxide, potassium hydroxide, and sodium hydroxide. Can be used. The catalyst is added in an amount of 0.000.00 mol per mol of the organic silicone compound based on the total amount of the organic silicone compound (37) and the optionally added organic silicone compound (42).
The amount is 1 to 1 mol, preferably 0.002 to 0.7 mol, and more preferably 0.003 to 0.4 mol. Even if the amount of the catalyst added is more than 1 mol, there is no particular economical advantage as compared with the effect of the addition.

When a weak acid such as acetic acid or malic acid is used as a catalyst, the reaction temperature is preferably in the range of 40 ° C. to 100 ° C. However, when a strong acid such as sulfuric acid or nitric acid is used as a catalyst, The range of 10 to 60 ° C is good. When phosphoric acid is used as a catalyst, the reaction can be performed at 10 ° C to 90 ° C. In the process of preparing the composition used in the SG method, and in the process of applying and drying the composition on an aluminum substrate, heat is often applied. However, when a volatile acid is used as a catalyst, the volatile acid volatilizes in peripheral devices. It may adhere and corrode it. When the present method is used in a step mainly using iron as a raw material, it is preferable to use nonvolatile sulfuric acid and / or phosphoric acid as a catalyst.

As described above, the composition comprising the organosilicone compound represented by the general formulas (37) and (42), the organic solvent, water and, if necessary, the catalyst is mixed with an appropriate reaction temperature, reaction time, In some cases, if a suitable stirring condition is selected and reacted, a polycondensation reaction occurs along with hydrolysis to produce a polymer or a colloidal polymer containing a Si-O-Si bond, and the viscosity of the liquid composition increases, Become
When preparing a sol solution using both the organosilicon compounds represented by the general formulas (37) and (42), both organosilicon compounds may be loaded into the reaction vessel from the beginning of the reaction, or The hydrolysis and polycondensation reaction may be advanced to some extent only by adding the other organosilicone compound to terminate the reaction. When the sol liquid used in the SG method is left at room temperature, the polycondensation reaction may continue to proceed and gel. Therefore, the sol liquid once prepared by the above method is diluted in advance with a solvent to be used for dilution at the time of application to an aluminum substrate, thereby preventing or delaying the gelation of the sol liquid. .

In both the SC method and the SG method, in order to bond a desired amount of an organosilicone compound or an addition-reactive functional group to a support, or to prepare an organosilicone compound or an addition-reactive functional group on the support. In order to eliminate the distribution unevenness, it is preferable to adjust the concentration by adding a solvent before applying these treatment liquids to the support. Alcohols, especially methanol, are preferred as solvents for this purpose, but other solvents, organic compounds,
Inorganic additives, surfactants and the like can also be added.

Examples of other solvents include methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propyl acetate, dimethoxyethane, methyl lactate, ethyl lactate, acetylacetone, Ethylene glycol and the like can be mentioned.
Examples of organic compounds that can be added include epoxy resins, acrylic resins, butyral resins, urethane resins, novolak resins, pyrogallol-acetone resins, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl methyl ether, polypropylene glycol, and the like. Examples of inorganic additives include colloidal silica,
Colloidal alumina and the like can be mentioned.

High-boiling solvents such as ethylene glycol and ethylene glycol monomethyl ether enhance the stability of the solution diluted to the concentration applied to the support, and the reproducibility of the reaction of the addition-reactive functional group bound to the support. Work to guarantee. Organic compounds such as a novolak resin and a pyrogallol-acetone resin have the same effect, but have a side effect of reducing the hydrophilicity of the surface of the obtained support, and it is necessary to finely adjust the addition amount.

When a sol solution or a liquid composition suitable for the SG method is applied to the surface of an aluminum substrate and then air-dried or heated and dried, the inorganic polymer formed of the Si—O—Si bond is gelled, Covalently bond. The drying is performed to volatilize the solvent, residual water and optionally the catalyst, but the step can be omitted depending on the purpose of use of the treated substrate. Also in the SC method, this drying step has the meaning of ensuring the close contact between the organosilicone compound and the aluminum substrate in addition to the volatilization of the solvent, residual water and the like. Therefore, depending on the purpose, after the drying is completed, the temperature may be further increased and the heating may be continued.

The maximum temperature during drying and, optionally, subsequent heating is preferably in such a range that the addition-reactive functional group R ¹⁸ is not decomposed. Therefore, drying temperature conditions that can be used are room temperature to 200 ° C., preferably room temperature to 150 ° C.
° C, more preferably room temperature to 120 ° C. The drying time is generally from 1 second to 30 minutes, preferably from 5 seconds to 10 minutes, more preferably from 10 seconds to 3 minutes. As a method of applying the liquid composition (organic silicone compound or its solution or sol solution) used in the present invention, various types such as brush coating, dip coating, atomizing, spin coating, doctor blade coating, and the like can be used. The thickness is determined in consideration of the shape of the surface of the aluminum substrate, the required film thickness to be processed, and the like. Before the aluminum substrate is subjected to the above-mentioned hydrophilic treatment with silicate, the substrate surface treatment described below is appropriately performed.

(Graining treatment) Graining methods include mechanical graining, chemical etching and electrolytic graining as disclosed in JP-A-56-28893. Furthermore, an electrochemical graining method of electrochemically graining in a hydrochloric acid or nitric acid electrolyte, a wire brush graining method in which the aluminum surface is scratched with a metal wire, and a ball in which the aluminum surface is grained with a polishing ball and an abrasive. A mechanical graining method such as a grain method, a brush grain method for graining the surface with a nylon brush and an abrasive can be used, and the above graining methods can be used alone or in combination.

Among them, a method for producing a surface roughness usefully used in the present invention is an electrochemical method in which the surface is chemically sanded in a hydrochloric acid or nitric acid electrolyte, and a suitable current density is 100 C / dm. It is in the range of ^{2 to} 400 C / dm ² . More specifically, in the electrolytic solution containing from 0.1 to 50% hydrochloric acid or nitric acid, the temperature 20 to 100 ° C., for 1 second to 30 minutes, electrolysis at a current density of 100C / dm ² ~400C / dm ² Is preferably performed.

The aluminum substrate thus grained is chemically etched with an acid or an alkali. When an acid is used as an etching agent, it takes time to destroy a fine structure, which is disadvantageous in industrially applying the present invention. However, it can be improved by using an alkali as an etching agent. Alkali agents suitably used in the present invention are caustic soda, sodium carbonate,
Sodium aluminate, sodium metasilicate, sodium phosphate,
Preferred ranges of concentration and temperature are 1 to 50% and 20 to 100 ° C., respectively, using potassium hydroxide, lithium hydroxide or the like.
It is preferable that the conditions are such that the amount of Al dissolved is 5 to 20 g / m ³ .

After the etching, pickling is performed in order to remove dirt (smut) remaining on the surface. As the acid used, nitric acid, sulfuric acid, phosphoric acid, chromic acid, hydrofluoric acid, borofluoric acid and the like are used. In particular, as a method for removing the smut after the electrochemical surface-roughening treatment, it is preferable to use a method of removing 50 to 50 as described in JP-A-53-12739.
A method of contacting with sulfuric acid of 15 to 65% by weight at a temperature of 90 ° C. and a method of alkali etching described in Japanese Patent Publication No. 48-28123 are exemplified.

(Anodic Oxidation Treatment) It is preferable that the aluminum substrate treated as described above is further subjected to an anodic oxidation treatment. The anodizing treatment can be performed by a method conventionally performed in this field. Specifically, sulfuric acid,
Phosphoric acid, chromic acid, oxalic acid, sulfamic acid, benzenesulfonic acid, etc. or a combination of two or more of these forms an anodized film on the surface of an aluminum support when direct or alternating current is passed through aluminum in an aqueous or non-aqueous solution. be able to.

The conditions of the anodic oxidation treatment vary depending on the electrolytic solution used, and thus cannot be determined unconditionally. However, in general, the concentration of the electrolytic solution is 1 to 80%, the liquid temperature is 5 to 70 ° C., and the current density is 0.5-60 amps / dm ² , voltage 1-100V,
An electrolysis time of 10 to 100 seconds is appropriate. Among these anodizing treatments, in particular, British Patent No. 1,412,7
No. 68, a method of anodizing at a high current density in sulfuric acid, and a method of anodizing phosphoric acid as an electrolytic bath described in US Pat. No. 3,511,661 are preferred. . In the present invention, the anodized film is preferably from ^{1~10g / m 2, 1g / m} 2 plate to easily enter the wound is not more than, 10 g / m ² or more is great power is required for the production Is economically disadvantageous. Preferably, it is 1.5 to 7 g / m ² . More preferably, 2-
5 g / m ² .

Further, in the present invention, after the graining treatment and the anodic oxidation, the aluminum substrate may be subjected to a sealing treatment. Such a sealing treatment is performed by immersing the substrate in hot water and a hot aqueous solution containing an inorganic salt or an organic salt, a steam bath, or the like.

The above-mentioned photopolymerizable photosensitive layer is formed on a support obtained by subjecting the aluminum substrate to graining treatment, anodic oxidation treatment, silicate treatment, and acid treatment as described above, and further applying an adhesive layer. By doing so, the lithographic printing plate precursor of the present invention is manufactured, but an organic undercoat layer may be provided as necessary before coating the photosensitive layer. Water-soluble resins, for example, polyvinylphosphonic acid, polymers and copolymers having a sulfonic acid group in the side chain, polyacrylic acid, water-soluble metal salts (for example, zinc borate), or those undercoated with yellow dyes, amine salts, etc. Are also suitable.

Examples of the organic compound used in the organic undercoat layer include carboxymethyl cellulose, dextrin, gum arabic, phosphonic acids having an amino group such as 2-aminoethylphosphonic acid, and phenyl which may have a substituent. Organic phosphonic acids such as phosphonic acid, naphthylphosphonic acid, alkylphosphonic acid, glycerophosphonic acid, methylenediphosphonic acid and ethylenediphosphonic acid, optionally substituted phenylphosphoric acid, naphthylphosphoric acid, alkylphosphoric acid and glyceroline Organic phosphoric acid such as an acid, phenylphosphinic acid which may have a substituent,
Naphthyl phosphinic acid, organic phosphinic acids such as alkyl phosphinic acid and glycerophosphinic acid, amino acids such as glycine and β-alanine, and hydrochlorides of amines having a hydroxyl group such as hydrochloride of triethanolamine are selected from, You may mix and use 2 or more types.

This organic undercoat layer can be provided by the following method. That is, a method in which a solution obtained by dissolving the above organic compound in water or an organic solvent such as methanol, ethanol, or methyl ethyl ketone or a mixed solvent thereof is coated on an aluminum plate and dried, and a method in which water or methanol, ethanol, methyl ethyl ketone, or the like is used. A solution in which the above organic compound is dissolved in an organic solvent or a mixed solvent thereof is immersed in the aluminum substrate to adsorb the organic compound, and then washed with water or the like,
This is a method of drying to provide an organic undercoat layer. In the former method, a solution of the above organic compound having a concentration of 0.005 to 10% by weight can be applied by various methods. For example, any method such as bar coater coating, spin coating, spray coating, and curtain coating may be used. In the latter method, the concentration of the solution is 0.01 to 20% by weight, preferably 0.05 to 20% by weight.
-5% by weight, the immersion temperature is 20-90 ° C., preferably 25-50 ° C., and the immersion time is 0.1 second-20 minutes,
Preferably it is 2 seconds to 1 minute.

The pH of the solution used is adjusted by a basic substance such as ammonia, triethylamine or potassium hydroxide, or an acidic substance such as hydrochloric acid or phosphoric acid.
It can also be used in the range of ~ 12. Further, a yellow dye can be added for improving the tone reproducibility of the lithographic printing plate precursor. The coating amount of the organic undercoat layer after drying is 2 to
200 mg / m ² is suitable, preferably 5 to 100 mg / m ^2.
a m ^2. If the coating amount is less than 2 mg / m ² , sufficient printing durability cannot be obtained. The same is true even if it is larger than 200 mg / m ² . The aluminum support may be further subjected to a surface treatment such as immersion in an aqueous solution of potassium fluoride zirconate, phosphate or the like.

[Oxygen-Blocking Protective Layer] The lithographic printing plate precursor of the present invention is usually provided with an oxygen-blocking protective layer on the photopolymerizable photosensitive layer since exposure is usually performed in the air. preferable. The oxygen-blocking protective layer prevents low-molecular compounds such as oxygen and basic substances present in the atmosphere, which inhibit the image forming reaction caused by exposure in the photosensitive layer, from being mixed into the photosensitive layer. Is possible. Therefore, a desired property of such a protective layer is that the permeability of low molecular compounds such as oxygen is low, and further, the transmission of light used for exposure is not substantially inhibited, and the adhesion to the photosensitive layer is excellent. In addition, it is desirable that it can be easily removed in a developing step after exposure.

Examples of the water-soluble vinyl polymer contained in the oxygen-barrier protective layer include polyvinyl alcohol and its partial esters, ethers and acetals, or a substantial amount of a water-soluble polymer required for imparting the necessary water solubility. Copolymers containing substituted vinyl alcohol units are included. As the polyvinyl alcohol, 71 to 10
One having 0% hydrolysis and having a degree of polymerization in the range of 300 to 2400 is exemplified. Specifically, Kuraray's PVA
-105, PVA-110, PVA-117, PVA-
117H, PVA-120, PVA-124, PVA-
124H, PVA-CS, PVA-CST, PVA-H
C, PVA-203, PVA-204, PVA-20
5, PVA-210, PVA-217, PVA-22
0, PVA-224, PVA-217EE, PVA-2
20, PVA-224, PVA-217EE, PVA-
217E, PVA-220E, PVA-224E, PV
A-405, PVA-420, PVA-613, L-8
And the like. As the above copolymer, 88 to 10
Examples include 0% hydrolyzed polyvinyl acetate chloroacetate or propionate, polyvinyl formal and polyvinyl acetal, and copolymers thereof. Other useful polymers include polyvinylpyrrolidone, gelatin and gum arabic, which may be used alone or in combination.

The solvent used for coating the oxygen-barrier protective layer of the present invention is preferably pure water, but alcohols such as methanol and ethanol, and ketones such as acetone and methyl ethyl ketone may be mixed with pure water. . The concentration of the solid content in the coating solution is suitably from 1 to 20% by weight. Known additives such as a surfactant for improving coating properties and a water-soluble plasticizer for improving physical properties of a film may be added to the oxygen-barrier protective layer of the present invention. Examples of the water-soluble plasticizer include propionamide, cyclohexanediol, glycerin, and sorbitol. Further, a water-soluble (meth) acrylic polymer or the like may be added. The amount of clothing is about 0.1 by weight after drying.
A range of from about / m ² to about 15 / m ² is suitable. More preferably, it is about 1.0 / m ² to about 5.0 / m ² .

The lithographic printing plate precursor thus obtained was
r laser, the second harmonic of semiconductor laser (SHG-L
D, 350-600 nm), YAG-SHG laser,
He-Ne laser (633, 543, 364 nm),
Ar laser (515,488 nm), FD-YAG laser (532 nm), InGaN semiconductor laser (3
(60-450 nm, especially 405 nm) and then developed. As a developing solution used for such a developing process, a conventionally known alkaline aqueous solution can be used. For example, sodium silicate, potassium, tribasic sodium, potassium, ammonium, dibasic sodium, potassium, ammonium, sodium carbonate, potassium, ammonium, sodium bicarbonate, potassium, potassium And inorganic alkali agents such as ammonium, sodium borate, potassium, ammonium, sodium hydroxide, ammonium, potassium, and lithium. Also, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolan, diisopropanolamine,
Organic alkali agents such as ethyleneimine, ethylenediamine and pyridine are also used.

These alkaline agents may be used alone or in combination of two or more.
Used in combination above. Of the above alkaline aqueous solution
Of these, a developer in which the effects of the present invention are further exhibited is
An aqueous solution containing potassium metal silicate and having a pH of 12 or more.
You. The aqueous solution of alkali metal silicate is a silicate component
Some silicon oxide SiO_TwoAnd alkali metal oxide M_TwoO ratio
Rate (typically [SiO_Two] / [M_TwoO]) and
Developability can be adjusted by the density.
As disclosed in JP-A-54-62004, S
iO_Two/ Na_TwoWhen the molar ratio of O is 1.0 to 1.5 (that is, [Si
O_Two] / [Na_TwoO] is 1.0 to 1.5 and SiO_Twoof
An aqueous solution of sodium silicate having a content of 1 to 4% by weight,
As described in JP-B-57-7427,
[SiO _Two] / [M] is 0.5 to 0.75 (that is, [SiO_Two]
/ [M_TwoO] is 1.0 to 1.5) and SiO_TwoThe concentration of
1 to 4% by weight and the developer is present therein
At least 2 based on gram atoms of all alkali metals
Alkali comprising 0% potassium
Metal silicates are preferably used.

Further, the planographic printing plate was prepared using an automatic developing machine.
When developing a master plate, the alkali strength is higher than that of the developer.
By adding a high aqueous solution (replenisher) to the developer,
Without replacing the developer in the development tank for a long time,
It is known that lithographic printing plate precursors can be processed
ing. This replenishment system is also preferably applied in the present invention.
Is done. For example, disclosed in Japanese Patent Application Laid-Open No. 54-62004.
[SiO 2_Two] / [Na_TwoO]
When the molar ratio is 1.0 to 1.5 (that is, [SiO_Two] / [Na_TwoO]
Is 1.0 to 1.5), and SiO_TwoContent of 1 to
Using an aqueous solution of 4% by weight of sodium silicate, and
Continuous or depending on the throughput of the positive photosensitive lithographic printing plate
Intermittent SiO_Two/ Na_TwoO molar ratio is 0.5 to 1.5
(Ie [SiO_Two] / [Na_TwoO] is 0.5 to 1.5)
For adding sodium silicate aqueous solution (replenisher) to the developer
And further disclosed in JP-B-57-7427.
[SiO_Two] / [M] is 0.5 to 0.75 (immediately
And [SiO_Two] / [M_TwoO] is 1.0 to 1.5)
And SiO_TwoAlkali metal having a concentration of 1 to 4% by weight
Alkali used as replenisher using silicate developer
Metal silicate [SiO _Two] / [M] is from 0.25 to 0.
75 (ie [SiO_Two] / [M_TwoO] is 0.5 to 1.5)
And both the developer and the replenisher are
Based on gram atoms of all alkali metals present in
Contains at least 20% potassium
The following development method is suitably used.

The lithographic printing plate thus developed is described in JP-A-54-8002 and JP-A-55-115045.
As described in JP-A-59-58431 and the like, post-treatment is carried out with washing water, a rinsing solution containing a surfactant and the like, and a desensitizing solution containing gum arabic and a starch derivative. In the post-treatment of the lithographic printing plate precursor according to the invention, these treatments can be used in various combinations. The lithographic printing plate obtained by such a process is set on an offset printing machine and used for printing a large number of sheets. As a plate cleaner used to remove stains on the plate during printing,
Conventionally known plate cleaners for PS plates are used, for example, CL-1, CL-2, CP, CN-
4, CN, CG-1, PC-1, SR, IC (manufactured by Fuji Photo Film Co., Ltd.) and the like.

[0259]

EXAMPLES The present invention will be described in more detail with reference to Synthesis Examples, Examples and Comparative Examples, which should not be construed as limiting the scope of the present invention. Synthesis Example 1 Unsaturated Group-Containing Diol Compound (44) In a 300 ml three-necked round bottom flask equipped with a condenser and a stirrer, 23.0 g (0.19 mol) of 2-amino-2-ethyl-1,3-propanediol was added. ) Is THF100m
l. Using a dropping funnel, 30.0 g (0.19 mol) of 2-isocyanateethyl methacrylate was added dropwise over 30 minutes, and the mixture was further stirred at room temperature for 8 hours. Thereafter, the solvent was distilled off under reduced pressure using a rotary evaporator to obtain 53 g of an oily compound (44). NM
R and mass spectrometry confirmed that it was compound (44).

Synthesis Example 2 Polyurethane Resin 20 5.2 g of the compound (44) and 10.4 g of 2,2-bis (hydroxymethyl) butanoic acid were placed in a 500 ml three-necked round bottom flask equipped with a condenser and a stirring group. 0.070 mol), polypropylene glycol (average molecular weight 100
0) 10.0 g (0.010 mol) was dissolved in 100 ml of N, N-dimethylacetamide. 4,4'-
20.5 g of diphenylmethane diisocyanate (0.0
82 mol), hexamethylenediisocyanate 3.5
g (0.021 mol), and heated and stirred at 100 ° C. for 5 hours, then N, N-dimethylformamide 200
and 400 ml of methyl alcohol. The reaction solution was poured into 4 liters of water while stirring to precipitate a white polymer. The polymer was separated by filtration, washed with water, and dried under vacuum to obtain 42 g of a polymer. Gel permeation chromatography (GP)
When the molecular weight was measured in C), the weight average (polystyrene standard) was 85,000. Furthermore, by titration,
When the carboxyl group content (acid value) was measured, it was 1.2.
It was 9 meq / g.

In the same manner as in Synthesis Example 2, a polyurethane resin of the present invention was synthesized using the diisocyanate compounds and diol compounds shown in Table 3. Further, the molecular weight was measured by GPC, and the acid value was measured by titration. Table 3 shows the measurement results. You can do it.

[0262]

[Table 3]

[0263]

[Table 4]

[0264]

[Table 5]

[0265]

[Table 6]

[0266]

[Table 7]

[0267]

[Table 8]

[0268]

[Table 9]

[0269]

[Table 10]

[0270]

[Table 11]

[0271]

[Table 12]

[Examples 1 to 10 and Comparative Examples 1 to 4] An aluminum plate of material 1S having a thickness of 0.30 mm was grained with a No. 8 nylon brush and an aqueous suspension of 800 mesh pamiston, and the surface thereof was grained. After that, it was washed well with water. 1
After etching by immersing in 0% sodium hydroxide at 70 ° C. for 60 seconds, the substrate was washed with running water, then neutralized with 20% HNO ₃ , and washed with water. This was subjected to electrolytic surface roughening treatment in a 1% nitric acid aqueous solution at an anode-time electricity quantity of 300 coulomb / dm ² using a sinusoidal alternating waveform current under the condition of V _A = 12.7 V. The surface roughness was measured to be 0.45 μm (Ra
Display). After immersion in a 30% H ₂ SO ₄ aqueous solution and desmutting at 55 ° C. for 2 minutes,
The cathode was placed on the grained surface in a 20% H ₂ SO ₄ aqueous solution at 20 ° C., and anodized at a current density of 5 A / dm ² for 50 seconds to obtain a thickness of 2.7 g / m ² .

Next, an undercoat solution was prepared according to the following procedure. The following composition was weighed into a beaker and stirred at 25 ° C. for 20 minutes.

Si (OC ₂ H ₅ ) ₄ 38 g 3-methacryloxypropyltrimethoxysilane 13 g 85% phosphoric acid aqueous solution 12 g Deionized water 15 g Methanol 100 g

The solution was transferred to a three-necked flask, fitted with a reflux condenser, and the three-necked flask was immersed in an oil bath at room temperature. The contents of the three-necked flask were heated to 50 ° C. in 30 minutes while stirring with a magnetic stirrer. While maintaining the bath temperature at 50 ° C., the reaction was further performed for 1 hour to obtain a liquid composition. This solution was diluted with methanol / ethylene glycol = 20/1 (weight ratio) so as to be 0.5% by weight, applied to an aluminum substrate with a wheeler, and dried at 100 ° C. for 1 minute. The coating amount at that time was 3.0 mg / m ² .
With respect to this coating amount, the amount of Si element was obtained by a fluorescent X-ray analysis method, and the obtained amount was used as the coating amount. On the thus treated aluminum plate, a photopolymerizable composition having the following composition was applied to a dry coating weight of 1.5 g / m ² and dried at 120 ° C. for 1 minute to form a photosensitive layer. .

[Photopolymerizable Composition] NK Oligo U-4H 2.0 g [(4-functional urethane acrylate) (Shin-Nakamura Chemical Co., Ltd.)] 2.0 g of polyurethane resin binder (B1) in Table 4 CGI- 784 [bis (cyclopentadienyl) 0.4 g-bis (2,6-difluoro-3- (pyr-1-yl)) titanium) (Ciba Specialty Chemicals Co., Ltd.)] 1,3-dibutyl -5- [7- (N, N-diethylamino) 0.1 g -4-methyl-2H-chromen-2-ylidene] -2-thioxo-4,6- (1H, 3H, 5H) pyrimidinedione 2- Methyl-4 '-(methylthio) -2-morpholino 0.4 g propiophenone-O- (P-vinylbenzyloxy) carbonylmethyloxime ε-phthalocyanine / (B1) dispersion 0.2 g Fluorine nonionic surfactant Megafac F176 0.03g (Dainihon I · The Chemical Industries, Ltd.) Cupferron AL / TCP (plasticizer) 0.05 g [1/9 (nitroso compounds, manufactured by Wako Pure Chemical)] Methyl ethyl ketone 30.0 g Propylene glycol 30.0 g monomethyl ether acetate

On this photosensitive layer, a 5% by weight aqueous solution comprising the following composition was applied so as to have a dry coating weight of 2.5 g / m ² and dried at 120 ° C. for 2 minutes to have an oxygen barrier layer. A lithographic printing plate precursor for laser exposure was obtained.

[Composition for Oxygen Blocking Layer] Kuraray Poval PVA-105 95% by weight Polyvinyl alcohol (degree of saponification 98% by mole, degree of polymerization 500) Polyvinylpyrrolidone K30 5% by weight (Wako Pure Chemical Industries, Ltd.)

Using a plate setter CELIC8200CTP (Ar laser (488 nm)) manufactured by Fuji Photo Film Co., Ltd., these plates were focused on the plate surface with 0.2 mJ / cm ² energy and 175 lines / inch.
Under a condition of 2540 dpi, a halftone image of 1 to 99% was simultaneously exposed. Thereafter, development processing was carried out using an automatic developing machine LP850P-II manufactured by Fuji Photo Film Co., Ltd. using the following developing solution and finisher solution. Developer: LP-D manufactured by Fuji Photo Film Co., Ltd. was diluted 9 times with water, and the liquid temperature was 25 ° C.
H = 12.8. Finisher: FP-2W manufactured by Fuji Photo Film Co., Ltd.
The gum solution was diluted three times with water.

The printing plate produced in this way was used as a printing machine with a two-color machine SOR-KZ manufactured by Heidelberg Co., Ltd.
As the ink, Claf G (N) manufactured by Dainippon Ink and Chemicals, Inc.
Was used to print 120,000 sheets. The extent to which 2% of 175 lines / inch reproduced on the printed matter was evaluated as the printing durability. The results are shown in Table 4.

[0281]

[Table 13]

From Table 4, it can be seen that when a urethane binder having an ethylenically unsaturated polymerizable group in the side chain obtained by a step of reacting at least a diisocyanate compound and a diol compound having an ethylenically unsaturated polymerizable group is used. It was found that the printing durability of the highlighted portion was high, while the printing durability of the highlighted portion was weak when a urethane binder having no polymerizable group or a binder not containing a polyurethane resin was used.

[0283]

The lithographic printing plate precursor according to the present invention is obtained by reacting at least a diisocyanate compound and a diol compound having an ethylenically unsaturated polymerizable group as a binder component on the photopolymerizable photosensitive layer. By containing the polyurethane, high sensitivity and excellent printing durability and stain resistance, particularly excellent highlight characteristics could be obtained.

Continued on the front page F-term (reference) 2H025 AA01 AA12 AA13 AA14 AB03 AC01 AC08 AD01 BC13 BC31 BC66 BC83 2H096 AA06 BA05 BA06 EA02 4J011 QA01 QA03 QA08 QB23 QB24 SA01 SA04 SA05 SA06 SA21 SA25 SA31 SA51 SA53 SA54 SA01 SA51 SA84 SA01 SA01 AG01 AG03 AG04 AG09 AG13 AG23 AG24 AG27 BA04 CB03 CB10 CC07 CD08 CD10

Claims (1)

[Claims] 1. An aluminum support comprising, on an aluminum support, an alkali-soluble urethane binder having an ethylenically unsaturated polymerizable group on a side chain, a compound having an addition-polymerizable ethylenically unsaturated double bond, and a photopolymerization initiator. A lithographic printing plate precursor comprising a photopolymerizable photosensitive layer, wherein the urethane binder is a reaction product of a diisocyanate compound and a diol compound having an ethylenically unsaturated polymerizable group.