JP2002144749A - Original plate for lithographic printing plate requiring no damping water - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an original plate for a lithographic printing plate requiring no damping water which shows high shelf stability, high sensitivity to a writing laser and a high-safety recording layer generating no harmful substance during recording. SOLUTION: This original plate for the lithographic printing plate requiring no damping water comprises a photothermal conversion layer for converting a laser light to heat and a silicone rubber layer laminated, in that order, on a support. The photothermal conversion layer is characterized in that it contains a photothermal conversion agent and a polyurethane which has at least one kind of a carboxyl group and uses a diol compound and an isocyanate compound as raw materials and is compounded at such a molar ratio of 1.03 or less of an isocyanate group of the isocyanate compound to the total amount of a hydroxyl group of the diol compound and a hydroxyl group contained in the moisture of a reaction system.

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 that does not require a dampening solution by heat mode recording using a laser beam (hereinafter, appropriately referred to as a lithographic plate precursor without water). In particular, the present invention relates to a waterless planographic plate having good storage stability and high sensitivity.

[0002]

2. Description of the Related Art In a conventional printing method using a lithographic printing plate which requires a dampening solution, it is difficult to control a delicate balance between the dampening solution and the ink, causing emulsification of the ink or mixing of the ink with the dampening solution. As a result, the ink has a large problem, such as poor ink density and background fouling, resulting in waste of paper. In contrast, waterless lithographic plates have many advantages because they do not require fountain solution. For example, Japanese Patent Publication No. 44-23042 and Japanese Patent Publication No. 46-160 relate to a waterless lithographic plate for performing lithographic printing without using dampening water.
44, JP-B-54-26923, JP-B-56-14
976, JP-B-56-23150, JP-B-61-5
No. 4222, JP-A-58-215411, JP-A-2-
Various types have been proposed in, for example, Japanese Patent Application Laid-Open No. 16561 and JP-A-2-236550.

On the other hand, in recent years, with the rapid progress of output systems such as prepress systems, imagesetters, and laser printers, printed images have been converted into digital data, and computer toe plates, computer toe plates, and the like.
A method of obtaining a printing plate by a new plate making method such as a cylinder has been proposed. Accordingly, new types of printing materials for these printing systems have been desired and are being developed. An example in which a waterless lithographic plate can be formed by writing using a laser beam is disclosed in Japanese Patent Publication No.
9, JP-A-50-158405, JP-A-6-557
No. 23, JP-A-6-186750, US Pat.
No. 705 and WO-9401280. These are sequentially provided on a support with a light-to-heat conversion layer containing a light-to-heat conversion agent such as carbon black and a self-oxidizing binder such as nitrocellulose, and an ink-repellent silicone rubber layer. It is described that a part is removed to make the area ink-adhesive and to perform waterless printing. However, in these light-to-heat conversion layers, nitrocellulose and a self-oxidizing nitrogen-containing compound such as ammonium nitrate are used as thermal decomposition compounds, and the carbon black in the light-to-heat conversion layer absorbs laser light and generates heat. When the light-to-heat conversion layer is destroyed,
Decomposition of nitrocellulose generates harmful gases such as nitrogen oxides, which is not preferable for environmental health.

In order to solve the environmental problems caused by the thermally decomposable nitrogen-containing compound such as nitrocellulose, Japanese Patent Application No. Hei 11
No. 373622 proposes a laser-writable waterless lithographic plate containing a light-to-heat conversion layer containing a polyurethane resin and a light-to-heat conversion agent. However, in this plan,
The storage stability of the lithographic printing plate precursor without water fluctuates depending on the synthesis conditions of the polyurethane resin, and depending on the synthesis conditions,
When stored for a long period of time, there is a problem that the photothermal conversion layer and the silicone rubber layer may peel off.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a waterless lithographic printing plate precursor having good storage stability without deterioration or reduction in sensitivity even when stored for a long period of time. Another object of the present invention is to provide a waterless lithographic plate having a highly safe recording layer that is highly sensitive to a writing laser and does not generate harmful substances during recording.

[0006]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the above object can be achieved by using a specific polyurethane for the light-to-heat conversion layer, and completed the present invention. That is, the fountain solution-free lithographic printing plate precursor of the present invention is a fountain solution-free lithographic printing plate precursor obtained by laminating a photothermal conversion layer for converting laser light into heat and a silicone rubber layer in this order on a support. The light-to-heat conversion layer has a light-to-heat conversion agent, and at least one carboxyl group, and a diol compound and an isocyanate compound as raw materials.
It is characterized by containing polyurethane synthesized in such a ratio that the molar ratio of the isocyanate group of the isocyanate compound to the total amount of the hydroxyl group of the diol compound and the hydroxyl group contained in the water in the reaction system is 1.03 or less. And

Since the lithographic printing plate precursor according to the present invention does not contain a self-oxidizing compound such as nitrocellulose in the light-to-heat conversion layer, it does not violently burn or destroy by laser irradiation, and is free from harmful substances such as nitrogen oxides. Does not occur. In addition, during the synthesis of polyurethane, by suppressing the molar ratio of isocyanate groups to hydroxyl groups in the reaction system to be low, it is possible to reduce the amount of excess diisocyanate compounds, particularly the amount of impurities derived from diisocyanate compounds that do not participate in polymerization can be reduced. In addition, since the light-to-heat conversion layer uses a polyurethane having a carboxyl group, the decomposition temperature of the light-to-heat conversion layer is lowered, and the adhesive force between the silicone rubber layer and the light-to-heat conversion layer in the laser irradiation part is efficiently reduced. As a result, it is considered that a highly sensitive waterless planographic plate can be obtained.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The waterless lithographic printing plate precursor of the present invention is obtained by sequentially laminating a light-to-heat conversion layer and a silicone rubber layer on a support. However, if these two layers are formed in this order, there is no particular limitation on the layer constitution. As long as the effects of the present invention are not impaired,
An intermediate layer, an overcoat layer, a backcoat layer and the like can be provided according to the purpose.

[Light-to-heat conversion layer] The feature of the waterless planographic printing plate precursor of the present invention resides in the light-to-heat conversion layer. That is, the light-heat conversion layer is (A)
It has at least one kind of carboxyl group, and uses an alcohol compound and an isocyanate compound as raw materials, and the molar ratio of the isocyanate group of the isocyanate compound to the total amount of hydroxyl groups contained in the alcohol compound and the water in the reaction system is 1 0.03 or less (hereinafter, referred to as a specific polyurethane having a carboxyl group) and (B) a photothermal conversion agent as an essential component, and optionally other compounds are used in combination. Can be. First, the light-to-heat conversion layer will be described.

(A) Specific polyurethane having a carboxyl group The polyurethane used in the present invention comprises (a) at least one diisocyanate compound, and a compound represented by the formula (1), (2) or
A structural unit represented by at least one kind of a diol compound represented by (3) (hereinafter referred to as (ii) a diol compound having a carboxyl group) and / or (c) tetracarboxylic dianhydride is added to (d) ) Polyurethanes having a basic skeleton of a structural unit which is a reaction product of a structural unit derived from a compound opened with a diol compound.
In the present invention, (a) a diol compound having a carboxyl group that reacts with a diisocyanate compound and (c) tetracarboxylic dianhydride are opened with a (d) diol compound. Compound "
Collectively referred to as diol compounds.

The compounds constituting the specific polyurethane (A) having a carboxyl group according to the present invention will be described. (A) Isocyanate compound The following are mentioned as (A) isocyanate compound which can be used in the present invention. Diisocyanate compound OCN-L ¹ -NCO (4) in formula represented by the following general formula (4), L ¹ represents an aliphatic or aromatic hydrocarbon group which may have a substituent. If necessary, L ¹ may have another functional group which 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 (4) include the following. That is, 2,4-tolylene diisocyanate, 2,4-
Dimer of tolylene diisocyanate, 2,6-tolylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 3,3'- Dimethylbiphenyl-
Aromatic diisocyanate compounds such as 4,4'-diisocyanate; aliphatic diisocyanate compounds such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate, etc .; isophorone diisocyanate, 4,4'-methylene bis (cyclohexyl) Alicyclic diisocyanate compounds such as isocyanate), methylcyclohexane-2,4 (or 2,6) diisocyanate, 1,3- (isocyanatomethyl) cyclohexane; 1 mol of 1,3-butylene glycol and 2 mol of tolylene diisocyanate And a diisocyanate compound which is a reaction product of a diol and a diisocyanate, such as an adduct of the compound.

(B) Diol compound having a carboxyl group In the present invention, the (B) diol compound constituting the urethane having a carboxyl group includes a diol compound represented by the formula (1):
Compounds obtained by ring-opening a structural unit represented by at least one of the diol compounds (2) and (3) and / or (c) tetracarboxylic dianhydride with a (d) diol compound.

[0013]

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Where R^TwoIs a hydrogen atom, a substituent (for example,
Cyano, nitro, halogen atom, (-F, -Cl, -B
r, -I), -CONH_Two, -COOR^Three, -OR^Three, −
NHCONHR^Three, -NHCOOR^Three, -NHCOR^Three,
-OCONHR^Three(Where R ^ThreeIs an alkyl having 1 to 10 carbon atoms
And a aralkyl group having 7 to 15 carbon atoms. )Such
Each group of is included. Alkyl) optionally having
Represents aralkyl, aryl, alkoxy, aryloxy groups
And preferably a hydrogen atom, an alkyl having 1 to 8 carbon atoms,
It represents an aryl group having 6 to 15 carbon atoms. L⁷, L⁸, L⁹
May be the same or different, each represents a single bond,
Groups (eg, alkyl, aralkyl, aryl, alk
Xy and halogeno groups are preferred. )
Represents a divalent aliphatic or aromatic hydrocarbon group and is preferably
Or an alkylene group having 1 to 20 carbon atoms, 6 to 15 carbon atoms
Arylene groups, more preferably 1 to 8 carbon atoms
Shows an alkylene group. If necessary, L⁷, L⁸, L⁹
In other functional groups that do not react with isocyanate groups, such as
Carbonyl, ester, urethane, amide, ureido,
It may have an ether group. Note that R^Two, L⁷, L⁸,
L⁹Two or three of which are joined together to form a ring
You may. Ar is a trivalent aromatic optionally having a substituent
And represents an aromatic hydrocarbon group, preferably having 6 to 15 carbon atoms.
Shows an aromatic group.

Specific examples of the diol compound having a carboxyl group represented by formula (1), (2) or (3) include the following. 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-
Dihydroxyethyl glycine, N, N-bis (2-hydroxyethyl) -3-carboxy-propionamide and the like.

(C) Tetracarboxylic dianhydride In the present invention, the preferred (C) tetracarboxylic dianhydride used in the synthesis of the polyurethane resin is represented by the following formulas (5), (6) and (7). What is shown is mentioned.

[0017]

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In the formula, L ¹⁰ 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 -,} - O- or -S- are shown, preferably a single bond, a divalent aliphatic hydrocarbon group having 1 to 15 carbon _{atoms, -CO -, - SO 2 -} , - O- or -S- is shown. 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 a hydrogen atom, an alkyl having 1 to 8 carbons, and a carbon number of 6 Represents up to 15 aryl, C1 to C8 alkoxy or halogeno groups. Also, two of L ¹⁰ , R ⁴ and R ⁵ may combine to form a ring.

R ⁶ and R ⁷ may be the same or different,
It represents a hydrogen atom, an alkyl, an aralkyl, an aryl or a halogeno group, preferably 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 ¹⁰ , R ⁶ and R ⁷ may combine to form a ring. L ¹¹ and L ¹² may be the same or different and represent a single bond, a double bond, or a divalent aliphatic hydrocarbon group, preferably 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.

The compound represented by the formula (5), (6) or (7) specifically includes the following compounds. 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 (Dai Nippon Ink Chemical Industry Co., Ltd., Epicron B-4)
Alicyclic tetracarboxylic acids such as 400), 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride and tetrahydrofurantetracarboxylic dianhydride Acid dianhydride; aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride and 1,2,4,5-pentanetetracarboxylic dianhydride;

These (c) tetracarboxylic dianhydrides are ring-opened by a (d) diol compound, and a reaction product of a structural unit derived from the resulting compound and (a) an isocyanate compound is obtained. Forming the basic skeleton of the polyurethane having a carboxyl group according to the present invention. As a method for introducing a structural unit derived from a compound obtained by ring-opening the (c) tetracarboxylic dianhydride with the (d) diol compound into the polyurethane resin, for example, the following method is available. a) A method of reacting (c) an alcohol-terminated compound obtained by ring-opening a tetracarboxylic dianhydride with a (d) diol compound and (a) a diisocyanate compound. b) ring opening of the diisocyanate compound (a) with the diol compound (d), the resulting compound is reacted under excess conditions, and the alcohol-terminated urethane compound obtained is reacted with (c) tetracarboxylic acid diacid. A method of reacting with an anhydride.

The (d) diol compounds used when (c) the tetracarboxylic dianhydride is used in the synthesis of the polyurethane according to the present invention specifically include 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, bisphenol A Propylene oxide adduct, 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 can be mentioned.

Other Diol Compounds Further, in the synthesis of the polyurethane having a carboxyl group of the present invention, other diol compounds having no carboxyl group can be used in combination. As the diol compound, broadly, a polyether diol compound, a polyester diol compound, a polycarbonate diol compound and the like can be mentioned. Examples of the polyether diol compound include formulas (8), (9), (10), (11), and (1)
The compound represented by 2), and a random copolymer of ethylene oxide and propylene oxide each having a hydroxyl group at a terminal are exemplified.

[0025]

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In the formula, R ¹ represents a hydrogen atom or a methyl group, and X represents the following groups. A, b, c, d, e,
f and g each represent an integer of 2 or more, preferably 2 to
It is an integer of 100.

[0027]

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Specific examples of the polyether diol compounds represented by formulas (8) and (9) 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, and polyethylene glycol having a weight average molecular weight of 2,000 Polyethylene glycol having a weight average molecular weight of 3000, polyethylene glycol having a weight average molecular weight of 7,500, 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, and polypropylene glycol having a weight average molecular weight of 2,000. Polypropylene glycol having an average molecular weight of 3000, polypropylene glycol having a weight average molecular weight of 4000, and the like.

Specific examples of the polyetherdiol compound represented by the formula (10) include the following. PTMG650, PTMG manufactured by Sanyo Chemical Industries, Ltd.
1000, PTMG2000, PTMG3000 and the like.

Specific examples of the polyether diol compound represented by the formula (11) include the following. New Pole PE-61 manufactured by Sanyo Chemical Industry Co., Ltd.
New Pole PE-62, New Pole PE-64, New Pole PE-68, New Pole PE-71, New Pole PE-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 formula (12) 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 (13) and (14).

[0034]

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In the formula, L ² , L ³ and L ⁴ may be the same or different and each represents a divalent aliphatic or aromatic hydrocarbon group, and L ⁵ represents a divalent aliphatic hydrocarbon group. . Preferably, L ² , L ³ , and L ⁴ each represent an alkylene group or an arylene group, and L ⁵ represents an alkylene group. L ² ,
In L ³ , L ⁴ and L ⁵ , other functional groups which do not react with the isocyanate group, for example, ether, carbonyl, ester, cyano, olefin, urethane, amide, ureido group or halogen atom 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 formula (15).

[0037]

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In the formula, L ⁶ may be the same or different and represents a divalent aliphatic or aromatic hydrocarbon group. Preferably, L ⁶ represents an alkylene group or an arylene group. In L ⁶ , other functional groups that do not react with isocyanate groups, such as ether, carbonyl, ester, cyano,
Olefins, urethanes, amides, ureido groups or halogen atoms may be present. n3 is an integer of 2 or more, and preferably an integer of 2 to 100.

Specific examples of the diol compound represented by the formula (13), (14) or (15) include the following. N in a specific example is an integer of 2 or more.

[0040]

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[0041]

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[0042]

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[0043]

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Further, similarly to the diol compound, the amino group-containing compounds represented by the following formulas (16) and (17) are reacted with the diisocyanate compound represented by the general formula (4) to form a urea structure. May be incorporated into the structure of the polyurethane resin.

[0045]

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In the formula, R ¹⁸ and R ¹⁹ 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, a carboxyl group). An alkyl group, an aralkyl group, or an aryl group, which may have a hydrogen atom, and preferably a carbon atom having 1 to 8 carbon atoms which may have a carboxyl group as a substituent. Alkyl represents an aryl group having 6 to 15 carbon atoms. L ²⁴ represents a substituent (eg, 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 ²⁴ may have another functional group that does not react with an isocyanate group, for example, a carbonyl, ester, urethane, or amide group. Two of R ¹⁸ , L ²⁴ and R ¹⁹ may be bonded to each other to form a ring.

Specific examples of the compounds represented by formulas (16) and (17) include the following. That is, ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, dodecamethylenediamine, propane-
1,2-diamine, bis (3-aminopropyl) methylamine, 1,3-bis (3-aminopropyl) tetramethylsiloxane, piperazine, 2,5-dimethylpiperazine, N- (2-aminoethyl) piperazine, 4-amino-2,2-6,6-tetramethylpiperidine, N, N
-Dimethylethylenediamine, lysine, L-cystine,
Aliphatic diamine compounds such as isophorone diamine;
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-phenylenediamine, 4,4′-diaminophenylether Aromatic diamine compounds such as 1,8-naphthalenediamine and the like; 2-aminoimidazole, 3-aminotriazole, 5-amino-1H-tetrazole, 4-aminopyrazole, 2-aminobenzimidazole, 2-amino-5 -Carboxy-triazole, 2,4-diamino-6-methyl-S-triazine,
Heterocyclic amine compounds such as 2,6-diaminopyridine, L-histidine, DL-tryptophan, adenine and the like; 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-amino-1-
Naphthol, 4-aminosalicylic acid, 4-hydroxy-
Amino alcohol or aminophenol compounds such as N-phenylglycine, 2-aminobenzyl alcohol, 4-aminophenethyl alcohol, 2-carboxy-5-amino-1-naphthol, L-tyrosine and the like.

The polyurethane resin having a carboxyl group according to the present invention is synthesized by adding the above-mentioned isocyanate compound and diol-based compound to a known catalyst having an activity corresponding to their respective reactivities and heating. It is known that the reaction solvent and the diol compound contain water depending on the humidity in the atmosphere when handling. On this occasion,
Since the isocyanate compound reacts with the water contained in the reaction solvent or the alcohol component, in order to synthesize a polyurethane resin having a desired composition, the water content in the solvent and the alcohol is measured, and according to the water content, It is necessary to determine the amount of the diisocyanate compound to be added. The molar ratio of the isocyanate group contained in the diisocyanate compound to the molar amount of the hydroxyl group of the diol compound and the hydroxyl group contained in the solvent and the water contained in the diol is 1.03 or less, and preferably in the range of 0.70 to 1.03. And more preferably in the range of 0.90 to 1.02, and most preferably in the range of 0.95 to 1.01. When the synthesis is performed in this range, a polyurethane which can form a highly stable light-to-heat conversion layer suitable for the purpose of the present invention can be obtained. When the isocyanate group remains at the polymer terminal of the polyurethane synthesized in this ratio range, the polyurethane is finally synthesized in a form in which the isocyanate group does not remain by treating with an alcohol or an amine. If the number of isocyanate groups exceeds this range, low molecular weight impurities derived from diisocyanate compounds that cannot participate in polymerization are mixed into the polyurethane. It is easy to induce delamination.

Among the diol compounds of the carboxyl group-containing polyurethane used in the present invention, the diol component having a carboxyl group accounts for 50% to 50% of the total diol component.
100%, preferably 60% to 95%. The content of the specific polyurethane having a carboxyl group used in the present invention is 30 to 30% in the total solids constituting the light-to-heat conversion layer.
90% by weight, preferably 40-85% by weight, more preferably 50-80% by weight.

(B) Photothermal conversion agent As the photothermal conversion agent used in the present invention, a known substance having a function of converting laser light used for writing into heat (photothermal conversion function) can be used. When the light source is an infrared laser, various organic and inorganic materials that absorb light at the wavelength used for the writing laser, such as infrared absorbing pigments, infrared absorbing dyes, infrared absorbing metals, and infrared absorbing metal oxides, can be used. It has been known for some time.

Examples of these light-to-heat converting agents include various carbon blacks such as acidic carbon black, basic carbon black and neutral carbon black, various carbon blacks surface-modified or coated to improve dispersibility, and nigrosine. , Black pigments such as aniline black and cyanine black, phthalocyanine, naphthalocyanine-based green pigments, carbon graphite, aluminum, iron powder, diamine-based metal complexes, dithiol-based metal complexes, phenolthiol-based metal complexes, and mercaptophenol-based metal complexes , Aryl aluminum metal salts, inorganic compounds containing water of crystallization, copper sulfate, chromium sulfide, silicate compounds, and metal oxides such as titanium oxide, vanadium oxide, manganese oxide, iron oxide, cobalt oxide, tungsten oxide, indium tin oxide Etc., hydroxides of these metals, sulfates, further bismuth, tin, tellurium, iron, adding an additive such as metal powder of aluminum preferred. Besides this,
"Infrared sensitizing dyes" as organic dyes (Matsuoka, Plenum Pres
s, New York, NY (1990)), US Pat. No. 4,833,124,
EP-321923, US Pat. No. 4,772,583, US Pat. No. 4,942,141, US Pat.
No. 6, US Pat. No. 4,948,777, US-494
No. 8778, US Pat. No. 4,950,639, US Pat.
No. 4912083, US Pat. No. 4,952,552,
Examples include various compounds described in the specification such as US Pat. No. 5,023,229, but are not limited thereto.

Of these, carbon black is particularly preferred from the viewpoints of light-to-heat conversion, economic efficiency, and handleability. Carbon black includes furnace black, lamp black, channel black,
Roll black, disc black, thermal black, acetylene black, etc. are classified, furnace black is variously used in terms of particle size and other aspects are commercially available, and it is preferably used because it is commercially inexpensive. You.

The degree of aggregation of the primary particles of carbon black affects the sensitivity of the printing plate. When the degree of aggregation of the primary particles of carbon black is high (having a high structure structure), the blackness of the plate material does not increase when compared with the same amount of addition, and as a result, the absorption rate of the laser beam decreases, and as a result, The sensitivity decreases. In addition, the viscosity of the coating solution for the light-to-heat conversion layer increases due to the aggregation of the particles, and the coating solution becomes thixotropy, so that the handling of the coating solution becomes difficult and the coating film becomes nonuniform. On the other hand, when the oil absorption is low, the dispersibility of the carbon black decreases, and the plate material sensitivity also tends to decrease. The degree of agglomeration of the primary particles of the carbon black can be compared by a value called oil absorption. The higher the oil absorption, the higher the degree of aggregation, and the lower the oil absorption, the lower the degree of aggregation. That is, it is preferable to use carbon black having an oil absorption of 20 to 200 ml / 100 g, more preferably
It is 40-120 ml / 100 g.

Further, carbon black having various particle sizes is commercially available, and the particle size of the primary particles also affects the plate material sensitivity. If the average particle size of the primary particles is too small, the light-to-heat conversion layer itself becomes transparent and cannot efficiently absorb laser light, resulting in a reduction in plate material sensitivity. If the particle size is too large, the particles are not dispersed at a high density, the blackness of the light-to-heat conversion layer is not increased, and the laser light cannot be efficiently absorbed, and the plate material sensitivity is also lowered. That is, it is preferable to use carbon black having an average primary particle diameter in the range of 10 to 50 nm, and more preferably 15 to 40 nm.

Further, conductive carbon black is used.
Thereby, plate material sensitivity can be improved. this
When the electrical conductivity is 0.01Ω^-1cm^-1~ 100Ω^-1
cm ^-1It is preferably in the range of, more preferably
0.1Ω^-1cm^-1-10Ω^-1cm^-1It is. Specifically
Are "CONDUCTEX" 40-220, "COND
UCTEX "975 BEADS," CONDUCTE
X "900BEADS," CONDUCTEX "SC,
“BATTERY BLACK” (Colombian Carbo
# 3000 (manufactured by Mitsubishi Chemical Corporation),
Nka Black ”(manufactured by Denki Kagaku Kogyo KK),“ VULCA
NXC-72R "(Cabot) is more preferred.
Often used.

As described above, the light-to-heat conversion layer of the present invention contains nitrogen by the thermal decomposition of nitro compounds such as nitrocellulose, ammonium nitrate, potassium nitrate, and sodium nitrate, and azo compounds, diazo compounds, and hydrazine derivatives. It is preferable from an environmental point of view not to include a self-oxidizing nitrogen-containing compound that generates an oxide. The amount of the light-to-heat conversion agent used in the present invention is 5 to 70% by weight, preferably 10 to 50% by weight, based on all solids constituting the light-to-heat conversion layer. When the addition amount is 5% by weight or less, the sensitivity decreases, and when the addition amount is 70% by weight or more, the film strength of the light-to-heat conversion layer decreases, and the adhesion to an adjacent layer also decreases.

In the light-to-heat conversion layer according to the present invention, a known binder that dissolves or disperses the light-to-heat conversion material may be used in addition to the above components (A) and (B). Examples thereof include homopolymers and copolymers of acrylic esters and methacrylic esters such as polymethyl methacrylate and polybutyl methacrylate, and homopolymers or copolymers of styrene monomers such as polystyrene and α-methylstyrene. Various synthetic rubbers such as isoprene and styrene-butadiene, homopolymers of vinyl esters such as polyvinyl acetate and copolymers such as vinyl acetate-vinyl chloride, and various condensation polymers such as polyurea, polyurethane, polyester, and polycarbonate; `` J. Imaging Sci., P59-64, 30 (2), (1986)
(Frechet et al.) "And" Polymers in Electronics (Sympo
sium Series, P11, 242, T. Davidson, Ed., ACS Washingto
n, DC (1984) (Ito, Willson) "," Microelectronic Eng
ineering, P3-10, 13 (1991) (E. Reichmanis, LFThompso
n)), a binder or the like used in a so-called “chemical amplification system” can be used. The addition amount thereof is 1 to 30% by weight based on the total solid content of the light-to-heat conversion layer.
5 to 20% by weight.

In the light-to-heat conversion layer according to the present invention, other known additives can be used in combination according to the purpose as long as the effects of the present invention are not impaired. These additives improve the mechanical strength of the light-to-heat conversion layer, improve the laser recording sensitivity, improve the dispersibility of the dispersion in the light-to-heat conversion layer, and improve the support, the primer layer and the silicone rubber layer. And the like are added according to various purposes such as improving the adhesion to an adjacent layer.

For example, in order to improve the mechanical strength of the light-to-heat conversion layer, various crosslinking agents for curing the light-to-heat conversion layer may be added. By adding this cross-linking agent, the light-to-heat conversion layer has a cross-linked structure.However, in the waterless lithographic original plate of the present invention, a polyurethane having a carboxyl group that forms the light-to-heat conversion layer is used. The carboxyl group becomes a reaction site at the time of crosslinking, and a dense crosslinked structure is formed. For this reason, even when development is performed using a developing solution containing a solvent, there is an advantage that a decrease in the adhesion of the non-image area can be effectively prevented. The crosslinking agent that can be used is not particularly limited, and a known crosslinking agent can be appropriately selected and used. Specifically, for example, a polyfunctional isocyanate compound or a polyfunctional epoxy compound, a hydroxyl group-containing compound, Examples thereof include a combination with an acid compound, a thiol-based compound, an amine-based compound, a urea-based compound, and the like, but are not limited thereto. The amount of the crosslinking agent used in the present invention is 1 to 30% by weight, preferably 2 to 20% by weight, based on the total solid content of the photothermal conversion layer. If the addition amount is less than 1% by weight, the effect of the addition of the crosslinking agent is insufficient, and if it exceeds 30% by weight, the film strength of the light-to-heat conversion layer becomes too strong and the plate material sensitivity is lowered.

When a pigment such as carbon black is used as the photothermal conversion agent, various pigment dispersants can be used as additives for improving the degree of dispersion of the pigment. The amount of the pigment dispersant used in the present invention is 1 to 70% by weight, preferably 5 to 50% by weight, based on the photothermal conversion agent.
It is. When the addition amount is less than 1% by weight, the effect of improving the degree of pigment dispersion is small and the plate material sensitivity is lowered, and when it exceeds 70% by weight, the adhesion to the adjacent layer is reduced.

In order to improve the adhesion to an adjacent layer, a known adhesion improver such as a silane coupling agent and a titanate coupling agent can be added. The addition amount of the adhesion improver used in the present invention is 5 to 30% by weight based on the total solid content of the light-to-heat conversion layer, preferably,
It is 10 to 20% by weight.

In order to improve the coating properties of the coating solution for the light-to-heat conversion layer, a surfactant such as a fluorine-based surfactant and a nonionic surfactant can be used as an additive.
The amount of the surfactant used in the present invention is 0.01 to 3% by weight, preferably 0.05 to 1% by weight, based on the total solid content of the photothermal conversion layer. In addition, various additives can be used as needed. The thickness of the photothermal conversion layer of the present invention is 0.05 to 10 μm, preferably 0.1 to 5 μm. The thickness of the light-to-heat conversion layer is 0.05μ
If it is less than m, sufficient optical density cannot be obtained, so that the laser recording sensitivity is lowered, and uniform film formation is difficult, and the image quality is deteriorated.

[Silicone Layer] The ink-repellent silicone rubber layer used in the present invention is formed by reacting a silicone rubber film on the photothermal conversion layer. Specifically, it is preferable to cure the condensation type silicone using a crosslinking agent or to form the addition type silicone by addition polymerization using a catalyst. When a condensation type silicone is used, (b) a condensation type crosslinking agent is used in an amount of 3 to 7 per 100 parts by weight of the diorganopolysiloxane.
It is preferable to use a composition to which 0 parts by weight and (c) 0.01 to 40 parts by weight of a catalyst are added.

The diorganopolysiloxane of the component (a) is a polymer having a repeating unit represented by the following general formula. R ¹ and R ² are an alkyl group having 1 to 10 carbon atoms, a vinyl group or an aryl group, and may have other suitable substituents. Generally, it is preferable that 60% or more of R ¹ and R ² be a methyl group, a halogenated vinyl group, a halogenated phenyl group, or the like.

[0067]

Embedded image

It is preferable to use a diorganopolysiloxane having hydroxyl groups at both ends. The component (a) has a number average molecular weight of 3,000 to 6,
00,000, more preferably 5,000 to 1
00,000. The crosslinking agent of the component (b) may be any one as long as it is of a condensation type, but is preferably one represented by the following general formula.

R ¹ _m · Si · X _n (m + n = 4, n is 2 or more)

Here, R ¹ has the same meaning as R ¹ described above, and X represents a halogen atom such as Cl, Br, I, a hydrogen atom, a hydroxyl group, or an organic substituent as shown below.

[0071]

Embedded image

In the formula, R ³ represents an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 20 carbon atoms, and R ⁴ and R ⁵ represent an alkyl group having 1 to 10 carbon atoms. As the component (c), a metal carboxylate such as tin, zinc, lead, calcium, or manganese, for example, a known catalyst such as dibutyl laurate, lead octylate, lead naphthenate, or chloroplatinic acid is used. No.

When using the addition type silicone,
(E) 0.1 to 25 parts by weight of an organohydrogenpolysiloxane and (f) based on 100 parts by weight of a diorganopolysiloxane having an addition-reactive functional group.
It is preferable to use a composition to which 0.00001 to 1 part by weight of the additional catalyst is added.

The diorganopolysiloxane having an addition-reactive functional group of the component (d) is an organopolysiloxane having at least two alkenyl groups (more preferably, vinyl groups) directly bonded to silicon atoms in one molecule. The alkenyl group may be at the molecular weight terminal or in the middle, and may have a substituted or unsubstituted alkyl or aryl group having 1 to 10 carbon atoms as an organic group other than the alkenyl group. Component (d) may optionally have a trace amount of hydroxyl groups. Component (d) has a number average molecular weight of 3,000 to 600,000, more preferably
5,000 to 100,000.

The component (e) includes polydimethylsiloxane having hydrogen groups at both terminals, α, ω-dimethylpolysiloxane, and (methylsiloxane)-
(Dimethylsiloxane) copolymer, cyclic polymethylsiloxane, polymethylsiloxane having trimethylsilyl groups at both terminals, dimethylsiloxane having trimethylsilyl groups at both terminals)-(methylsiloxane) copolymer, and the like.

The component (f) is arbitrarily selected from known polymerization catalysts, and is particularly preferably a platinum compound, such as platinum alone, platinum chloride, chloroplatinic acid, and olefin-coordinated platinum. .

For the purpose of controlling the curing rate of the silicone rubber layer in these compositions, organopolysiloxanes containing a vinyl group such as tetracyclo (methylvinyl) siloxane, alcohols containing a carbon-carbon triple bond, acetone, methyl ethyl ketone It is also possible to add a crosslinking inhibitor such as methanol, ethanol, propylene glycol monomethyl ether and the like. In the silicone rubber layer, if necessary, fine powders of inorganic substances such as silica, calcium carbonate and titanium oxide, silane coupling agents, adhesion aids such as titanate coupling agents and aluminum coupling agents, and photopolymerization. An initiator may be added.

[0078] thickness of the ink repellent silicone rubber layer in the present invention is preferably 0.5 to 5 g / m ² as dry film thickness, and more preferably from 1 to 3 g / m ^2. When the film thickness is less than 0.5 g / m ² , the ink repellency decreases, and there is a problem that the film is easily damaged. When the film thickness is more than 5 g / m ² , image reproducibility deteriorates.

In the lithographic original plate without water according to the present invention,
Various silicone rubber layers may be further coated on the silicone rubber layer for the purpose of improving printing durability, scratch resistance, image reproducibility, stain resistance, and the like.

Since the silicone rubber layer of the waterless planographic printing plate precursor of the present invention is flexible and easily scratched, a transparent film, for example, polyester such as polyethylene terephthalate and polyethylene naphthalate, polyethylene, , Polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, cellophane, etc., or a polymer coating. These films may be used after being stretched. Further, the surface may be subjected to mat processing, but from the viewpoint of image reproducibility, the case without the mat processing is preferable in the present invention.

[Support] The waterless lithographic plate of the present invention must have enough flexibility to be set in a normal printing machine and at the same time withstand the load applied during printing. Therefore, typical supports that can be used for the waterless lithographic original plate of the present invention include coated paper, metal plates such as aluminum, plastic films such as polyethylene terephthalate, rubber, and composites thereof. And more preferably coated papers, aluminum plates, aluminum-containing (eg, alloys with aluminum with metals such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, nickel, etc.) alloy plates and plastic films. . Further, two or more of these exemplified supports may be laminated or adhered with an adhesive or the like.

These supports have improved surface adhesion,
Various surface treatments such as a corona discharge treatment, a matt-easy adhesion treatment, and an antistatic treatment may be performed to improve the antistatic property. The thickness of the support is suitably from 25 μm to 3 mm, preferably from 75 μm to 500 μm, but the optimum thickness varies depending on the type of support used and printing conditions. Generally, 100 μm to 300 μm is most preferable.

[Primer Layer] In the present invention, a primer layer can be provided between the support and the photothermal conversion layer. As the primer layer used in the present invention, various layers can be used for improving the adhesion between the substrate and the light-to-heat conversion layer and improving the printing characteristics. For example, JP
Various types of photosensitive polymers as disclosed in JP-A-2-2903 are exposed and cured before laminating a photosensitive resin layer, and epoxy resins disclosed in JP-A-62-50760 are used. Heat cured, JP 6
Japanese Patent Application Laid-Open No. 3-133151 discloses a hardened gelatin disclosed in Japanese Patent Application Laid-Open No. 3-133151, a device using a urethane resin and a silane coupling agent disclosed in Japanese Patent Application Laid-Open No. 3-200965, and Japanese Patent Application Laid-Open No. 3-273248. And the like using a urethane resin disclosed in US Pat. In addition, those obtained by hardening gelatin or casein are also effective.

Further, for the purpose of softening the primer layer, polyurethane, polyamide, styrene / butadiene rubber, carboxy-modified styrene / butadiene rubber having a glass transition temperature of not more than room temperature,
Acrylonitrile / butadiene rubber, carboxy-modified acrylonitrile / butadiene rubber, polyisoprene, acrylate rubber, polyethylene, chlorinated polyethylene,
A polymer such as chlorinated polypropylene may be added.
The addition ratio is arbitrary, and the primer layer may be formed only by the additive as long as the film layer can be formed.

Further, these primer layers may be provided with a dye, a pH indicator, a printing-out agent, a photopolymerization initiator, and an adhesion assistant (for example, a polymerizable monomer, a diazo resin, a silane coupling agent, Additives such as titanate coupling agents and aluminum coupling agents), pigments, silica powder and titanium oxide powder can also be included, and after application, they can be cured by exposure. Generally, the coating amount of the primer layer is 0.1 to 10 by dry weight.
g / m ² is suitable, preferably 0.3 to 7 g.
/ M ² , more preferably 0.5 to 5 g / m ² . The waterless lithographic original plate of the present invention is obtained by forming a light-to-heat conversion layer and a silicone layer after providing a primer layer on the support as desired.

The waterless planographic printing plate precursor of the present invention is imagewise exposed and then developed to obtain a waterless planographic printing plate. In the present invention, the laser used for exposing the waterless lithographic plate gives an exposure amount necessary to cause a sufficient decrease in adhesion to cause the silicone rubber layer to be peeled off from the support. If there is no particular limitation,
Gas lasers such as an Ar laser and a carbon dioxide laser, solid lasers such as a YAG laser, and semiconductor lasers can be used. Usually, a laser having a power of 50 mW class or more is required. Semiconductor lasers and semiconductor-excited solid-state lasers (such as YAG lasers) are preferably used in terms of practicality such as maintainability and price. The recording wavelength of these lasers is in the infrared wavelength range,
Oscillation wavelengths from 00 nm to 1100 nm are often used. Exposure can also be performed using an imaging device described in JP-A-6-186750.

When a film for protecting the surface of the silicone rubber layer is provided as described above, the film may be exposed as it is if it is a light-transmitting film, or the film may be peeled off during laser exposure. Exposure may be performed later. Exposure with such an infrared laser reduces the adhesion between the support and the silicone rubber layer due to the reaction of the light-to-heat conversion layer in the exposed portion, and the ink repellent layer in the exposed portion is removed in the subsequent development step. Thus, an image area is formed as a parent ink area, and the silicone rubber layer in an unexposed area becomes a non-image area as an ink repellent area, thereby obtaining a lithographic printing plate requiring no dampening solution.

The developer used for making the waterless lithographic original plate of the present invention includes those known as developers for waterless lithographic original plates, such as hydrocarbons, polar solvents, water, and combinations thereof. Although it can be appropriately selected and used, from the viewpoint of safety, it is preferable to use water or an aqueous solution of an organic solvent containing water as a main component, and considering the safety and flammability, the concentration of the organic solvent in the developer is preferably Less than 40% by weight is desirable.

Examples of the hydrocarbons that can be used in the developer include aliphatic hydrocarbons [specifically, for example, hexane, heptane, gasoline, kerosene, and commercially available solvents such as “Isoper E, H, G” (Esso Chemical Co., Ltd.), aromatic hydrocarbons (eg, toluene, xylene, etc.), and halogenated hydrocarbons (trichlene, etc.). Also,
Examples of the polar solvent include alcohols (specifically, for example, methanol, ethanol, propanol, isopropanol, benzyl alcohol, ethylene glycol monomethyl ether, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl Ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, etc.), ketones (eg, acetone, methyl ethyl ketone, etc.), esters (eg, ethyl acetate, methyl lactate, Butyl lactate, propylene glycol monomethyl ether acetate, diethylene glycol Lumpur acetate, diethyl phthalate), other, triethyl phosphate, tricresyl phosphate and the like. Also, simply tap water,
Water itself such as pure water or distilled water can also be used. These may be used alone, for example, water may be added to hydrocarbons, water may be added to a polar solvent, or a combination of hydrocarbons and a polar solvent may be used in combination of two or more. .

Further, in preparing the developing solution, if a hydrocarbon or a polar solvent having low affinity for water is used, a surfactant or the like may be added to improve the solubility in water. . In addition, an alkali agent (for example, sodium carbonate, diethanolamine, sodium hydroxide, etc.) can be added together with the surfactant.

The development can be carried out by a known method, for example, by rubbing the plate surface with a developing pad containing the above-described developer, or by pouring the developer onto the plate and rubbing it with a developing brush in water. it can. The developer temperature can be any temperature, but is preferably from 10C to 50C. As a result, the silicone rubber layer, which is the ink repellent layer in the image area, is removed, and that area becomes the ink receiving area. The development processing described above, or the subsequent washing and drying processing, can also be performed by an automatic processor. A preferable example of such an automatic processor is described in JP-A-2-22661.

The lithographic original plate without water according to the present invention can be developed by bonding the adhesive layer to the surface of the silicone rubber layer and then peeling the adhesive layer. Any known adhesive layer that can be in close contact with the surface of the silicone rubber layer can be used. Those provided with these adhesive layers on a flexible support are commercially available, for example, under the trade name of "Scotch Tape # 851A" manufactured by Sumitomo 3M Limited. Also,
When printing plates thus processed are stacked and stored, it is preferable to insert and insert a slip sheet to protect the printing plates.

The waterless lithographic plate according to the present invention thus obtained is set in a predetermined printing machine and supplied with dampening water and ink to perform printing. Since the waterless lithographic original plate of the present invention has good storage stability, even if it is stored for a long period of time after production, it is possible to obtain many good printed matters without deterioration such as delamination or a decrease in sensitivity.

[0094]

EXAMPLES The present invention will be specifically described with reference to examples. However, the present invention is not limited to the following examples. [Synthesis Example 1: Polyurethane 1] In a 1000 ml three-necked round bottom flask equipped with a condenser and a stirrer, 2,2
-Bis (hydroxymethyl) propionic acid 30.0 g
(0.224 mol) and 24.9 g (0.025 mol) of polypropylene glycol (weight average molecular weight 1000) were dissolved in 340 g of N, N-dimethylacetamide to prepare a solution. Next, when the water content of this solution was measured with a Karl Fischer moisture meter MKC-210 manufactured by Kyoto Denshi, the water content was 0.076%. Therefore, this solution contained 0.30 g (0.016 mol) of water. Based on this, 64.9 g (0.259 mol) of 4,4′-diphenylmethane diisocyanate was used so that the molar ratio of the isocyanate group to the mole number of the hydroxyl group contained in the diol compound and the water in the system was 1.01. ) Was added and the mixture was heated and stirred at 60 ° C. for 2 hours. Then, N, N-
It was diluted with 200 ml of dimethylacetamide and 400 ml of methyl alcohol. The reaction solution was poured into water 41 with stirring to precipitate a white polymer. This polymer was separated by filtration, washed with water, and dried under vacuum to obtain 120 g of a white polymer (polyurethane 1). Gel permeation chromatography (GP
When the molecular weight was measured in C), it was 80,000 in weight average (polystyrene standard).

[Synthesis Example 2: Polyurethane 2] In the same apparatus as in Example 1, 2,2-bis (hydroxymethyl)
A solution obtained by dissolving 12.1 g (0.09 mol) of propionic acid and 20.0 g (0.01 mol) of a polyester diol compound (San Ester 24620; manufactured by Sanyo Chemical Co., Ltd.) in 100 g of N, N-dimethylacetamide Was prepared. As a result of measuring water in the same manner as in Synthesis Example 1,
The water content was 0.055%. Therefore, this solution contained 0.07 g (0.004 mol) of water. Based on this, the molar ratio of the isocyanate group to the molar number of the hydroxyl group contained in the diol compound and the water in the system is 1.00.
25.5 g (0.102 mol) of 4,4′-diphenylmethane diisocyanate was added so that
The mixture was heated and stirred at ℃ for 5 hours. Thereafter, the same post-treatment as in Synthesis Example 1 was performed to obtain a white polymer (polyurethane 2) 50
g was obtained. The molecular weight was measured by gel permeation chromatography (GPC) and found to be 50,000 in weight average (polystyrene standard).

Comparative Synthesis Example 1 Polyurethane 3 In a 1000 ml three-necked round bottom flask equipped with a condenser and a stirrer, 30.0 g (0.224 mol) of 2,2-bis (hydroxymethyl) propionic acid was added. And 24.9 g of polypropylene glycol (weight average molecular weight 1000)
(0.025 mol) in N, N-dimethylacetamide 3
The solution was dissolved in 40 g to prepare a solution. As a result of measuring water in the same manner as in Synthesis Example 1, the water content was 0.085.
%Met. Therefore, this solution contains 0.33 g of water.
(0.018 mol). Based on this, the molar ratio of isocyanate groups to the number of moles of hydroxyl groups contained in the diol compound and water in the system is 1.05,
4,4'-diphenylmethane diisocyanate 67.7
g (0.270 mol) was added, and the mixture was heated and stirred at 60 ° C. for 2 hours. Thereafter, the same post-processing as in Synthesis Example 1 was performed, and 1
20 g of a white polymer (polyurethane 3) were obtained. The molecular weight was measured by gel permeation chromatography (GPC) and found to be 50,000 in weight average (polystyrene standard).

(Examples 1 and 2, Comparative Example 1) [Formation of light-to-heat conversion layer] The following mixed solution was stirred with glass beads for 30 minutes in a paint shaker to disperse carbon black, and the glass beads were filtered off. Then, 0.2 parts by weight of a fluorine-based surfactant Megafac F177 (manufactured by Dainippon Ink and Chemicals, Inc.) was added and stirred to prepare a photothermal conversion layer coating solution. This coating solution was applied on a corona-treated transparent polyethylene terephthalate film having a thickness of 188 μm so as to have a dry film thickness of 1 μm, and dried by heating to form a photothermal conversion layer.

-75 parts by weight of polyurethane described in Table 1-25 parts by weight of carbon black (# 40 manufactured by Mitsubishi Carbon Co., Ltd.)-2 parts by weight of Solsperse S27000 (manufactured by ICI)-1000 parts by weight of propylene glycol monomethyl ether

[0099]

[Table 1]

[Formation of Silicone Rubber Layer] The following coating solution was applied on the light-heat exchange layer and heated (at 130 ° C., 1 ° C.).
Min) and dried to form an addition type silicone rubber layer having a dry film thickness of 2 μm. 9 parts by weight of α, ω-divinylpolydimethylsiloxane (degree of polymerization 500) 0.2 parts by weight of (CH ₃ ) ₃ SiO (SiH (CH ₃ ) O) ₈ —Si (CH ₃ ) ₃・ Olefin-platinum chloride 0.15 parts by weight of acid ・ Control agent [HC≡CC (CH ₃ ) ₂ —O—Si (CH ₃ ) ₃ ] 0.2 part by weight ・ Isopar G (manufactured by Esso Chemical Co., Ltd.) 120 parts by weight

A 12 μm-thick polyethylene terephthalate was laminated on the surface of the silicone rubber layer obtained as described above to obtain a waterless lithographic original plate covered with a cover fill of Examples 1 and 2 and Comparative Example 1.

[Measurement of Sensitivity] After the cover film of each of the waterless planographic masters obtained above was peeled off, a wavelength of 830 nm was obtained.
Using a semiconductor laser having an output power of 300 mW and a beam diameter of 32 μm (1 / e ² ), a continuous line was written at different writing speeds. Thereafter, the surface of the plate was wiped with a developing pad containing isopropanol to remove the silicone rubber layer in the laser-irradiated portion, and the plate surface energy at which the silicone rubber layer in the irradiated portion could be removed as a continuous line was determined as sensitivity. The measurement results are also shown in Table 1 above.

[Evaluation of Storage Stability] Each of the waterless planographic masters thus obtained was exposed to an environment at a temperature of 45 ° C. and a humidity of 75% for 7 days, and the same treatment as in the measurement of the sensitivity was performed. The state of the layer was observed, and a sample in which no peeling of the silicone rubber layer was observed in an unexposed portion was evaluated as ○, and a sample in which peeling was observed was evaluated as ×. The evaluation results are also shown in Table 1 above.

From the results shown in Table 1, the molar ratio of the isocyanate group of the isocyanate compound to the total amount of the hydroxyl group of the diol compound of the present invention and the hydroxyl group of the water contained in the reaction system is 1.03 or less. It was clear that the waterless lithographic printing plate precursor using the synthesized polyurethane-containing light-to-heat conversion layer had good storage stability and high sensitivity. On the other hand, when a polyurethane resin synthesized under the condition that the molar ratio of isocyanate groups is more than 1.03 is used, storage stability is poor,
It turned out to be a practical problem.

[0105]

The lithographic printing plate precursor requiring no dampening solution according to the present invention has excellent storage stability, high sensitivity when recording images with a heat mode laser, and no generation of harmful substances. It works. Further, by exposing and developing the lithographic printing original plate requiring no dampening solution, a lithographic printing plate requiring no dampening solution can be easily obtained.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor, Shizuka Hirano 4000F, Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Prefecture F-term in Fujisha Shin Film Co., Ltd. CC06 2H096 AA13 BA20 EA04 EA23 2H114 AA05 AA22 AA24 BA01 BA10 DA03 DA46 DA60 DA64 EA01 EA02 EA10 FA16

Claims (1)

[Claims] 1. A fountain solution-free lithographic printing plate precursor comprising a support, on which a photothermal conversion layer for converting laser light into heat and a silicone rubber layer are laminated in this order, wherein the photothermal conversion layer is a photothermal conversion layer. A converting agent, and the isocyanate having at least one kind of carboxyl group and using a diol compound and an isocyanate compound as raw materials, based on the total amount of hydroxyl groups of the diol compound and hydroxyl groups contained in water in the reaction system. A lithographic printing plate precursor requiring no dampening solution, comprising a polyurethane synthesized in such a ratio that the molar ratio of isocyanate groups of the compound becomes 1.03 or less.