JP2002287335A - Method for forming planographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for forming a planographic printing plate in which developability is not deteriorated when the planographic printing plate is formed by developing an original plate for the planographic printing plate capable of heat mode recording with laser light within 120 see after image exposure with laser light. SOLUTION: In the method for forming a planographic printing plate in which an original plate for the planographic printing plate having a heat sensitive layer containing carbon black and a binder polymer on the base and a hydrophilic or lipophobic layer on the heat sensitive layer is imagewise exposed with laser light and developed within 120 see to remove the hydrophilic or lipophobic layer in the exposed area, the dibutyl phthalate (DBP) oil absorption of the carbon black contained in the heat sensitive layer is >=90 ml/100 g.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for forming a lithographic printing plate capable of heat mode recording by laser light,
Furthermore, the present invention relates to a method for forming a lithographic printing plate, which can be developed in a short time within 120 seconds after image exposure with a laser beam and is applicable to an automated CTC type printing press.

[0002]

2. Description of the Related Art In general, a lithographic printing plate comprises an oleophilic image area for receiving ink during a printing process and a hydrophilic non-image area for receiving fountain solution. As such a lithographic printing plate precursor, a PS plate in which a lipophilic photosensitive resin layer is provided on a hydrophilic support has been widely used. As a plate making method, usually, after exposing through an image such as a lith film, a non-image portion is dissolved and removed with a developing solution, and a desired printing plate is obtained by this method.
The plate making process in the conventional PS plate requires an operation of dissolving and removing a non-image portion after exposure, and the need for or simplification of such an additional wet process is required in the prior art. This is one of the issues that have been desired to be improved. In particular, in recent years, the disposal of the waste liquid discharged by wet processing has become a major concern of the entire industry due to consideration for the global environment, and the demand for improvement in this aspect has been further increased.

[0003] As one of the simple plate making methods responding to this demand, an image recording layer is used in which a non-image portion of a printing plate precursor can be removed in a normal printing process. To obtain a final printing plate. The lithographic printing plate making method by such a method is called an on-press development method. As a specific method, for example, a method of using an image recording layer soluble in a fountain solution or an ink solvent, a method of performing mechanical removal by contact with an impression cylinder or a blanket cylinder in a printing press, and the like can be used. However, a major problem with the on-press development method is that the printing plate precursor has an image recording layer that is not fixed even after exposure.For example, the printing plate is stored in a completely light-shielded state or at a constant temperature until it is mounted on a printing press. It was necessary to take a time-consuming method of doing so.

On the other hand, another trend in this field in recent years is that the digitization technology for electronically processing, storing, and outputting image information using a computer has become widespread. Various new image output methods corresponding to the image forming technology have come into practical use. Along with this, a computer that carries digitized image information in highly convergent radiation such as laser light, scans and exposes an original plate with this light, and directly manufactures a printing plate without passing through a lith film -To-plate technology is attracting attention. Therefore, obtaining a printing plate precursor suitable for this purpose is an important technical problem. Against this background, simplification, dryness, and no-processing of plate making work have become more desirable than ever, both in terms of the above-mentioned environmental aspects and adaptation to digitalization. ing.

As a method of making a printing plate by scanning exposure which is easy to incorporate into the digitization technology, a solid-state laser such as a semiconductor laser or a YAG laser has recently become available at a low cost. Plate making methods using these lasers as image recording means have become promising. In the conventional plate making method, the photosensitive lithographic printing plate precursor is subjected to imagewise exposure at low to medium illuminance, and image recording is performed by changing the image-like physical properties of the plate surface due to a photochemical reaction. In the method using high power density exposure using a laser, a large amount of light energy is intensively irradiated in an exposure area during an instantaneous exposure time, and the light energy is efficiently converted to heat energy, and the heat energy is converted to heat energy. Causes a thermal change such as a chemical change, a phase change, a change in form or structure, and uses the change for image recording. That is, image information is input by light energy such as laser light, while image recording is recorded by a reaction by heat energy. Normally, a recording method using heat generated by such high power density exposure is called heat mode recording, and changing light energy to heat energy is called photothermal conversion.

A major advantage of the plate making method using the heat mode recording means is that the plate is not exposed to light having a normal illuminance level such as room illumination, and that an image recorded by high illuminance exposure does not require fixing. . In other words, if a heat mode photosensitive material is used for image recording, it is safe against room light before exposure, and it is not essential to fix an image after exposure. Therefore, for example, if an image recording layer that is insolubilized or solubilized by heat mode exposure is used, and a plate making process in which the exposed image recording layer is imagewise removed to form a printing plate is performed by an on-press development method, development (non-image Part removal) allows for a printing system in which the image is not affected for some time after image exposure, even if exposed to room ambient light. Therefore, the use of heat mode recording is expected to make it possible to obtain a lithographic printing plate precursor particularly desirable for an on-press development system.

[0007] As one of the preferable methods for producing a lithographic printing plate based on such heat mode recording, a hydrophilic layer or an oleophobic layer is provided on the heat mode recording layer, and the recording layer is exposed to heat in an image form. Has been proposed in which a hydrophilic layer or an oleophobic layer in an exposed portion is removed by ablation of the exposed portion, if necessary, by wet treatment.

[0008] As such a lithographic printing plate precursor,
For example, a configuration in which a hydrophilic layer or an oleophobic layer is provided on a heat-sensitive layer containing a laser light absorber such as carbon black and a self-oxidizing binder such as nitrocellulose, and the configuration in which the hydrophilic layer is provided is , WO 98/40212
Publication, WO98 / 34796, WO94 / 18
005, JP-A-6-199064, JP-A-8-282143, and the like, the configuration in which an oleophobic layer is provided is disclosed in JP-B-42-21879 and JP-A-50-15.
8405, JP-A-6-55723, JP-A-6-186750, U.S. Pat. No. 5,353,705
And WO / 9401280.

However, among these, a lithographic printing plate precursor having a heat-sensitive layer containing a laser light absorber and a binder polymer is immediately heated by laser exposure.
When the removal treatment (development treatment) of the hydrophilic layer or the oleophobic layer, which is the upper layer, is performed by rubbing or the like, after a sufficient time has passed after heating by laser exposure, the laser exposure is significantly more remarkable than when the removal treatment is similarly performed. There was a problem that the removability (developability) of the hydrophilic layer or the oleophobic layer in the portion was deteriorated. This is considered to be because the heat-sensitive layer after laser exposure is not sufficiently cooled and is processed in a softened state.

For example, Japanese Patent No. 2938398, Japanese Patent No. 2648081, US Pat. No. 5,755,158, EP8
No. 87204A, GB2297719A, etc., after mounting a lithographic printing plate precursor on a printing press cylinder, exposing by a laser mounted on the printing press, and then mounting on a printing press. The plate surface is washed (developed) with a plate surface washing device, or a fountain solution and / or
Alternatively, a so-called C is supplied to the plate surface and developed on the machine.
When a TC (Computer to Cylinder) type printing machine is applied, each process is automated and performed continuously, so the development process is performed within a relatively short time after laser exposure. Is done. For this reason, there has been a demand for a method of forming a lithographic printing plate which does not deteriorate in developability even in a development process in a short time after laser exposure and is applicable to a CTC type printing machine.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to form a lithographic printing plate by performing development processing within 120 seconds after exposing the lithographic printing plate precursor capable of heat mode recording by laser light to an image by laser light. It is an object of the present invention to provide a method of forming a lithographic printing plate which does not cause deterioration in developability.

[0012]

Means for Solving the Problems As a result of intensive studies, the present inventors have provided a heat-sensitive layer containing carbon black and a polymer binder on a support, and further provided a hydrophilic layer or a heat-sensitive layer on the heat-sensitive layer. In a lithographic printing plate precursor having an oleophobic layer, the lithographic printing plate precursor is imagewise laser-exposed by applying carbon black having a dibutyl phthalate (DBP) oil absorption of 90 ml / 100 g or more, Within 120 seconds, even if subjected to a development treatment for removal of the hydrophilic layer or the oleophobic layer of the laser exposure part,
They found that there was no deterioration in developability, and completed the present invention. Although the cause of the deterioration of the developability is not clear by performing the development processing before the elapse of sufficient time after the laser exposure, the heat-sensitive layer heated by the laser exposure is not sufficiently cooled, and Is considered to be the cause.

In the present invention, by using carbon black having a dibutyl phthalate (DBP) oil absorption of 90 ml / 100 g or more, deterioration in developability due to the heat history of the heat-sensitive layer heated by laser exposure is eliminated. . Although the reason is not clear, carbon black having a large DBP oil absorption has a high structure (degree of particle aggregation) of the particle aggregate, so that the binder polymer component in the heat-sensitive layer is easily absorbed into the aggregate. It is considered that the influence of the softening of the binder polymer due to heat is suppressed.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The basic configuration of a lithographic printing plate precursor (hereinafter, also referred to as a lithographic printing plate precursor of the present invention) used in the method of forming a lithographic printing plate of the present invention is such that at least DBP is provided on a support.
A heat-sensitive layer, a hydrophilic layer or an oleophobic layer containing carbon black having an oil absorption of 90 ml / 100 g or more and a binder polymer is laminated in this order. Further, the lithographic printing plate precursor of the present invention has a 120
Within seconds, a development process for removing the hydrophilic layer or the oleophobic layer in the laser-exposed area is performed to form a lithographic printing plate.

(Thermal Sensitive Layer) The thermosensitive layer used in the lithographic printing plate precursor according to the present invention has at least (1) a DBP oil absorption of 9
It contains 0 ml / 100 g or more of carbon black and (2) a polymer binder. Further, the heat-sensitive layer used in the lithographic printing plate precursor according to the present invention is such that when the upper layer of the laser-exposed portion is removed by development in the laser-exposed portion, the entire heat-sensitive layer of the laser-exposed portion is removed together with the upper layer, and the ink receiving layer is removed. The lower layer may be exposed, or a part of the heat-sensitive layer of the laser-exposed portion may be removed together with the upper layer, and a part may remain, and the remaining heat-sensitive layer may function as an ink receiving layer. Considering the necessity of imparting ink receptivity to the lower layer and lowering the sensitivity, an embodiment in which the heat-sensitive layer in the laser-exposed area remains is preferable. To do this,
The heat-sensitive layer is preferably ink-receptive and hardened with a crosslinking agent.

The carbon black used in the present invention is:
(1) Carbon black having a DBP oil absorption of 90 ml / 100 g or more.
The absorption amount of DBP per 100 g when dibutyl phthalate (DBP) is added to carbon black is shown using an SK6217 absorbometer. DBP
As described above, the oil absorption is an index indicating the structure of the carbon black particle aggregate, that is, the degree of particle aggregation. The larger the oil absorption is, the larger the particle aggregation is. For this reason,
Carbon black having a larger DBP oil absorption tends to contain an oily component inside the particle aggregate. The carbon black used in the present invention has a DBP oil absorption of 90 ml / 1.
It is important that the weight is at least 00 g, preferably 1 g.
10 ml / 100 g or more, more preferably 11
5 ml / 100 g or more, and considering the dispersion stability of carbon black and the like, 115 ml / 100 g to 250
ml / 100 g.

The carbon black used in the present invention is not particularly limited as long as the carbon black has a DBP oil absorption of 90 ml / 100 g or more. Any carbon black such as carbon black, basic carbon black and neutral carbon black can be used. The average primary particle size of the carbon black used in the present invention is preferably 5 to 200 nm, more preferably 10 to 100 nm, in consideration of the dispersibility in the heat-sensitive layer.

Specifically, for example, Mitsubishi Carbon Black # 990, MA600, # 40, # 40 manufactured by Mitsubishi Chemical Corporation
32, # 30, # 20, MA100, MA100R, M
A100S, MA200RB, MA230, # 4000
B, # 4350B, # 3030B, # 3040B, # 3
050B, # 3230B, # 3350B, # 3150,
# 3250, # 3600, # 3750, # 3950,
Toka Black # 8500, # 7 manufactured by Tokai Carbon Co., Ltd.
350, # 7100F, # 5500, # 4500, # 4
400, # 4300, # 3855, # 3845, Seast 3, Seast 6, Seast SO, Raven 3500 manufactured by Columbian Carbon Co., Ltd., and carbon black Printex 90, Printex 8 manufactured by Degussa Hüls
0, Printex30, SpecialBlack1
00, PrintexG, Printex40, Pri
ntex60, PrintexL6, Printex
L, Printex3, PrintexA, Print
exXE2, LampBlack101, XPB89
0, XPB890B, HiBlack30B, HiBl
ack30, HiBlack20B, HiBlack2
0, HiBlack10, HiBlack150B, H
iBlack40B1, HiBlack40B2, carbon black MONARCH 880 manufactured by Cabot Corporation,
MONARCH 460, MONARCH 280, MON
ARCH700, MONARCH1400, MONAR
CH1300, MONARCH1000, BLACK
PEARLS700, BLACK PEARLS88
0, BLACK PEARLS480, BLACK PE
ARLS460, BLACK PEARLS280, B
LACKPEARLS1300, BLACK PEAR
LS1000, VULCAN XC72, VULCAN
XC72R, VULCAN9A32, ELFTEX8,
ELFTEX PELLETS115, STERLIN
GV, STELLINGSO, Denki Kagaku Kogyo Co., Ltd.
Denka Black and the like.

The DBP oil absorption is 90 ml / 100
g or more of carbon black, even if used alone,
More than one species may be used in combination. The amount used is from 10% by weight to 70% by weight, preferably from 20% by weight to 60% by weight, more preferably from 25% by weight, based on the total solid weight of the heat-sensitive layer.
% To 50% by weight.

As the binder polymer (2) used in the present invention, a known polymer having a film forming ability and capable of dispersing the carbon black is used. Examples of these are nitrocellulose, cellulose such as ethyl cellulose, cellulose derivatives, polymethyl methacrylate, acrylic acid esters such as polybutyl methacrylate, homopolymers and copolymers of methacrylic acid esters, polystyrene, α-methyl styrene and the like. Homopolymers or copolymers of styrene monomers, isoprene, various synthetic rubbers such as styrene-butadiene, homopolymers of vinyl esters such as polyvinyl acetate and copolymers such as vinyl acetate-vinyl chloride, polyurea, Various condensed polymers such as polyurethane, polyester, and polycarbonate, and "J. Imaging Sc
i., P59-64, 30 (2), (1986) (Frechet et al.) "and" Polymer
s in Electronics (Symposium Series, P11, 242, TD
avidson, Ed., ACS Washington, DC (1984) (Ito, Willso
n) "," Microelectronic Engineering, P3-10, 13 (199
1) (E. Reichmanis, LFThompson) "and a binder or the like used in a so-called" chemical amplification system "can be used.

Among these, a polymer having a functional group which can be used for a crosslinking reaction for hardening the heat-sensitive layer with a crosslinking agent is preferable. Preferred functional groups include, for _{example, -OH, -SH, -NH 2,} -NH -, - CO-N
_{H 2, -CO-NH -,} - O-CO-NH -, - NH-
CO-NH-, -CO-OH, -CO-O-, -CO-
O-, -CS-OH, -CO-SH, -CS-SH,-
CO-O-CO -, - SO 3 H, -SO 2 (O -), - P
_{O 3 H 2, -PO (O} -) 2, -SO 2 -NH 2, -S0 2 -
_{NH -, - CO-CH 2} -CO -, - CH = CH -, -
_{CH = CH 2, -CO-CH} = CH 2, -CO-C (CH
₃ ) = CH ₂ ,

[0022]

Embedded image

And the like. Particularly, a hydroxyl group, an amino group, a carboxyl group, an epoxy group, and a polymerizable vinyl group are preferable. Preferred binder polymers of the present invention include, for example, acrylic acid, methacrylic acid and other monomers containing a carboxyl group, such as homopolymers or copolymers, hydroxyethyl methacrylate and 2-hydroxypropyl acrylate and other hydroxyl-containing acrylic acids. Or a homopolymer or copolymer of methacrylic acid ester, a homopolymer or copolymer of acrylic acid or methacrylic acid ester containing an epoxy group such as glycidyl methacrylate, a homopolymer or copolymer of N-alkylacrylamide or acrylamide. Homopolymer or copolymer of polymer, amine and glycidyl acrylate, glycidyl methacrylate or allyl glycidyl reaction product, p-hydroxystyrene, homopolymer or copolymer of vinyl alcohol, poly Urethane resins, polyurea resins, polyamide (nylon) resins, epoxy resins, polyalkylene imines, novolak resins,
Examples include condensates such as melamine resins and cellulose derivatives.

These polymers may be used alone or in combination of two or more. The amount used is 20% to 90% by weight, preferably 25% to 80% by weight, more preferably 30% to 75% by weight, based on the total solid weight of the heat-sensitive layer. As the crosslinking reaction used for the hardening of the heat-sensitive layer of the present invention, the formation of a covalent bond by heat or light, or the formation of an ionic bond by a polyvalent metal salt is possible. Hardening of the layers is also possible.

Known crosslinking agents include polyfunctional isocyanate compounds, polyfunctional epoxy compounds, polyfunctional amine compounds, polyol compounds, polyfunctional carboxyl compounds, aldehyde compounds, polyfunctional (meth) acrylic compounds, polyfunctional vinyl compounds, Functional mercapto compounds, polyvalent metal salt compounds, polyalkoxysilane compounds, polyalkoxytitanium compounds, polyalkoxyaluminum compounds, metal chelate compounds (titanium diisopropoxide bis (2,4-pentadionate), titanium diisopropoxide) Bis (ethyl acetoacetate), aluminum tris (2,4-pentadionate, etc.), polymethylol compounds, polyalkoxymethyl compounds, and the like. A known reaction catalyst can be added to accelerate the reaction. is there.

The amount used is from 0% by weight to 50% by weight, preferably from 3% by weight to 40% by weight, more preferably from 5% by weight to 35% by weight, based on the total solid weight in the coating solution of the thermosensitive layer. It is.

In the present invention, other additives can be used. These additives improve the mechanical strength of the heat-sensitive layer, improve the laser recording sensitivity, improve the dispersibility of carbon black in the heat-sensitive layer, and improve the properties of adjacent layers such as a support and an intermediate layer. It is added for various purposes such as improving the adhesion. For example, it is conceivable to add a known compound that decomposes by heating to generate a gas in order to improve laser recording sensitivity.
In this case, laser recording sensitivity can be improved due to rapid volume expansion of the heat-sensitive layer. As examples of these additives, azidodicarbonamide, sulfonylhydrazine, dinitrosopentamethylenetetramine and the like can be used.

Known compounds which decompose by heating to form acidic compounds can be used as additives. By using these together with a chemical amplification system binder, the decomposition temperature of the constituent material of the thermosensitive layer is greatly reduced,
As a result, laser recording sensitivity can be improved. Examples of these additives include various iodonium salts, sulfonium salts, phosphonium tosylate, oxime sulfonate, dicarbodiimide sulfonate, triazine and the like. Further, the degree of dispersion of carbon black in the heat-sensitive layer may affect laser recording sensitivity, and therefore, various pigment dispersants are used as additives. Further, a known adhesion improver (for example, a silane coupling agent, a titanate coupling agent, etc.) may be added to improve the adhesiveness. In addition, various additives are used as necessary, such as a surfactant for improving coating properties.

The heat-sensitive layer composition used in the present invention is, for example, 2-methoxyethanol, 2-methoxyethyl acetate, propylene glycol methyl ethyl acetate, methyl lactate, ethyl lactate, propylene glycol monomethyl ether, ethanol, isopropanol, methyl ethyl ketone. , N, N-dimethylformamide,
N, N-dimethylacetamide, tetrahydrofuran,
A suitable solvent such as dioxane or the like is dissolved or dispersed in a single solvent or a mixed solvent thereof, and the solution is coated on a substrate and dried.
The coating weight is the weight after drying, 0.1 to 10 g / m ^2.
It is suitable, and preferably from 0.3 to 5 g / m ^2, more preferably less than 0.5 g / m ² or more 3 g / m ^2. If the coating weight of the heat-sensitive layer after drying is lower than 0.1 g / m ² , undesired results such as a decrease in laser recording sensitivity and a decrease in ink receptivity are given, and the higher the amount, the higher the ink consumption tends to be. Is economically disadvantageous.

(Support) The support used in the lithographic printing plate precursor according to the present invention has a degree of flexibility that can be set in an ordinary printing press, and at the same time, is dimensionally resistant to the load applied during printing. It is a stable plate-like material. For example, paper, paper or metal plate laminated with plastic (eg, polyethylene, polypropylene, polystyrene, etc.), metal plate (eg, aluminum, zinc, copper, etc.), plastic film (eg, Cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene naphthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.) Deposited Paper was, or plastic film. The thickness of the support is from 25 μm to 3 m
m, preferably 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.

The support used in the lithographic printing plate precursor of the present invention is preferably a polyester film or an aluminum plate. Among them, an aluminum plate which has good dimensional stability and is relatively inexpensive is particularly preferable. Suitable aluminum plates are a pure aluminum plate and an alloy plate containing aluminum as a main component and a trace amount of a different element, and may be a plastic film on which aluminum is laminated or vapor-deposited. The foreign elements contained in the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, titanium and the like. The content of the foreign element in the alloy is at most 10% by weight or less. Particularly preferred aluminum in the present invention is pure aluminum. However, 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 an aluminum plate of a conventionally known and used material can be appropriately used.

In the present invention, in order to improve the adhesion between the support and the heat-sensitive layer and to improve the printing properties, the support may be subjected to surface modification by sandblasting or the like or surface modification by corona treatment or the like. An intermediate layer can be provided between the layer and the heat-sensitive layer. For example, the surface roughening of the aluminum plate can be performed as follows. Prior to roughening the aluminum plate, if necessary, a degreasing treatment with, for example, a surfactant, an organic solvent, or an alkaline aqueous solution is performed to remove rolling oil on the surface. The surface roughening treatment of the surface of the aluminum plate is performed by various methods, for example, a method of mechanically roughening the surface, a method of electrochemically dissolving the surface, and a method of selectively dissolving the surface chemically. It is performed by the method of causing. As a mechanical method, a known method such as a ball polishing method, a brush polishing method, a blast polishing method, and a buff polishing method can be used. Further, as an electrochemical surface roughening method, there is a method of performing an alternating or direct current in a hydrochloric acid or nitric acid electrolyte. Also, Japanese Patent Application Laid-Open No. Sho 54-639
As disclosed in Japanese Patent Laid-Open No. 02-203, a method in which both are combined can also be used.

The surface roughening by the above-mentioned method is carried out when the center line surface roughness (Ha) of the surface of the aluminum plate is 0.3 to 1.0.
It is preferable that the coating be performed within a range of μm. The roughened aluminum plate is subjected to an alkali etching treatment using an aqueous solution of potassium hydroxide or sodium hydroxide as necessary, and further neutralized, and then, if necessary, anodized to enhance abrasion resistance. Processing is performed. As the electrolyte used for the anodic oxidation treatment of the aluminum plate, various electrolytes that form a porous oxide film can be used, and generally, sulfuric acid, hydrochloric acid, oxalic acid, chromic acid, or a mixed acid thereof is used. The concentration of these electrolytes is appropriately determined depending on the type of the electrolyte.

The anodizing treatment conditions vary depending on the electrolyte used and cannot be specified unconditionally. However, in general, the concentration of the electrolyte is 1 to 80% by weight, the solution temperature is 5 to 70 ° C., and the current density is 5 to 60 A. / Dm ² , a voltage of 1 to 100 V, and an electrolysis time of 10 seconds to 5 minutes are appropriate. The amount of the anodic oxide film is 1.0 to 5.0 g / m ² , especially 1.5 to 4.0 g / m ² .
m ² is preferred. After the anodizing treatment, the aluminum surface is subjected to a hydrophilic treatment as necessary. Examples of the hydrophilic treatment used in the present invention include U.S. Pat. Nos. 2,714,066 and 3,181,461.
There is an alkali metal silicate (for example, sodium silicate aqueous solution) method as disclosed in 3,280,734 and 3,902,734. In this method, the support is immersed in an aqueous solution of sodium silicate or electrolytically treated. In addition, Japanese Patent Publication No. 36-220
No. 63,868, U.S. Pat. No. 3,276,868 and U.S. Pat.
For example, a method of treating with polyvinyl phosphonic acid as disclosed in 3,461 and 4,689,272 can be used.

As the intermediate layer used in the lithographic printing plate precursor according to the present invention, for example, various photosensitive polymers as disclosed in JP-A-60-22903 are used before the heat-sensitive layer is laminated. Exposure cured
The epoxy resin disclosed in JP-A-2-50760 cured by heat, the gelatin disclosed in JP-A-63-133151 hardened, and further disclosed in JP-A-3-200965. Using a urethane resin and a silane coupling agent as disclosed in
One using urethane resin disclosed in Japanese Patent No. 273248 can be mentioned. In addition, those obtained by hardening gelatin or casein are also effective.

Further, for the purpose of softening the intermediate layer, polyurethane, polyamide, styrene / butadiene rubber, carboxy-modified styrene / butadiene rubber, acrylonitrile / butadiene rubber, and acrylonitrile / butadiene rubber having a glass transition temperature of room temperature or lower are contained in the intermediate layer. Polymers such as carboxy-modified acrylonitrile / butadiene rubber, polyisoprene, acrylate rubber, polyethylene, chlorinated polyethylene and chlorinated polypropylene may be added. The addition ratio is arbitrary, and the intermediate layer may be formed with only the additive as long as it is within a range in which a film layer can be formed. In addition, these intermediate layers may have a dye, a pH indicator, a printing-out agent, a photopolymerization initiator, an adhesion aid (eg, a polymerizable monomer, a diazo resin, a silane coupling agent, etc.), a pigment, etc. And additives such as silica powder and titanium oxide powder. After the application, it can be cured by exposure. In general, the coating amount of the intermediate layer is suitably in the range of 0.1 to 10 g / m ² , preferably 0.3 to 8 g / m ² , more preferably 0.5 to 5 g / m ^{2 in} terms of dry weight. It is.

When a nonconductive material such as polyester is used for the support of the present invention, a polymer in which metal oxide fine particles or a matting agent is dispersed is used for the purpose of improving the adhesion between the heat-sensitive layer and the support and preventing electrification. It is preferred to provide an intermediate layer consisting of layers. As the material of the metal oxide particles used for the intermediate layer, SiO ₂ , ZnO, TiO ₂ , SnO ₂ ,
Al ₂ O ₃ , In ₂ O ₃ , MgO, BaO, MoO ₃ , V ₂ O
₅ and their composite oxides, and / or metal oxides further containing different atoms in these metal oxides. These may be used alone or as a mixture. As the metal oxide, SiO ₂ , ZnO, Sn
O ₂ , Al ₂ O ₃ , TiO ₂ , In ₂ O ₃ and MgO are preferred.

Examples of containing a small amount of heteroatoms include Al or In for ZnO and Sb, Nb for SnO ₂ .
Alternatively, a material obtained by doping a heteroatom such as Sn with an amount of 30 mol% or less, preferably 10 mol% or less with respect to a halogen element or In ₂ O ₃ can be used. The metal oxide particles are preferably contained in the intermediate layer in a range of 10 to 90% by weight. The average particle diameter of the metal oxide particles is preferably in the range of 0.001 to 0.5 μm. Here, the average particle diameter is a value including not only the primary particle diameter of the metal oxide particles but also the particle diameter of the higher-order structure.

The matting agent that can be used in the intermediate layer is preferably an inorganic or organic particle having an average particle size of 0.5 to 20 μm, more preferably an average particle size of 1.0 to 15 μm. No. As the inorganic particles, for example, metal oxides such as silicon oxide, aluminum oxide, titanium oxide, zinc oxide, calcium carbonate, barium sulfate,
Metal salts such as barium titanate and strontium titanate are exemplified. Examples of the organic particles include cross-linked particles of polymethyl methacrylate, polystyrene, polyolefin, and a copolymer thereof. The matting agent is preferably contained in the intermediate layer in a range of 1 to 30% by weight.

Examples of the polymer which can be used in the intermediate layer include proteins such as gelatin and casein; cellulose compounds such as carboxymethylcellulose, hydroxyethylcellulose, acetylcellulose, diacetylcellulose and triacetylcellulose; dextran, agar, sodium alginate, and the like. Saccharides such as starch derivatives, polyvinyl alcohol, polyvinyl acetate, polyacrylates, polymethacrylates, polystyrene,
Examples include synthetic polymers such as polyacrylamide, polyvinylpyrrolidone, polyester, polyvinyl chloride, polyacrylic acid, and polymethacrylic acid. The polymer is preferably contained in the intermediate layer in the range of 10 to 90% by weight.

The support used in the present invention preferably has a maximum roughness depth (Rt) of at least 1.2 μm on the back surface of the support from the viewpoint of preventing blocking. (I.e., the back surface of the lithographic printing plate precursor of the present invention) preferably has a dynamic friction coefficient (μk) of 2.6 or less when sliding on the surface of the lithographic printing plate precursor of the present invention. For this reason, it is preferable that the back surface of the support is provided with a layer containing the same matting agent as shown in the above-mentioned intermediate layer, or is subjected to sand blasting or the like to be roughened.

(Hydrophilic Layer) The hydrophilic layer usable in the present invention includes, for example, an organic hydrophilic matrix obtained by crosslinking or pseudo-crosslinking an organic hydrophilic polymer, polyalkoxysilane, titanate, zirconate, or the like. A layer containing an inorganic hydrophilic matrix or a thin film of a metal or metal compound having a hydrophilic surface obtained by a sol-gel conversion comprising a hydrolysis and condensation reaction of aluminate is preferred.

As the crosslinking reaction used for forming the organic hydrophilic matrix of the hydrophilic layer of the present invention, formation of a covalent bond by heat or light or formation of an ionic bond by a polyvalent metal salt is possible. As the organic hydrophilic polymer used in the present invention, a polymer having a functional group that can be used for a crosslinking reaction is preferable. Preferred functional groups include, for example,
_{-OH, -SH, -NH 2, -NH} -, - CO-NH 2,
-CO-NH-, -O-CO-NH-, -NH-CO-
NH-, -CO-OH, -CO-O-, -CO-O-,
-CS-OH, -CO-SH, -CS-SH, -SO 3
^{_{H, -SO 2 (O -)}} , - PO 3 H 2, -PO (O -) 2, -
SO ₂ —NH ₂ , —SO ₂ —NH—, —CH ＝ CH ₂ , —C
H = CH -, - CO- C (CH 3) = CH 2, -CO-C
H = CH ₂ , —CO—CH ₂ —CO—, —CO—O—CO
−,

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And the like.

Particularly, a hydroxyl group, an amino group, a carboxyl group and an epoxy group are preferred.

As such an organic hydrophilic polymer of the present invention, a known water-soluble binder can be used, for example, polyvinyl alcohol (a saponification degree of 60%).
Polyvinyl acetate), modified polyvinyl alcohol such as carboxy-modified polyvinyl alcohol, starch and derivatives thereof, carboxymethylcellulose and salts thereof, cellulose derivatives such as hydroxyethylcellulose, casein, gelatin, gum arabic, polyvinylpyrrolidone, vinyl acetate-crotonic acid Copolymer and its salt, styrene-maleic acid copolymer and its salt, polyacrylic acid and its salt, polymethacrylic acid and its salt,
Polyethylene glycol, polyethyleneimine, polyvinylphosphonic acid and its salt, polystyrenesulfonic acid and its salt, poly (methacryloyloxypropanesulfonic acid) and its salt, polyvinylsulfonic acid and its salt, poly (methacryloyloxyethyltrimethylammonium chloride) , Polyhydroxyethyl methacrylate,
Examples thereof include polyhydroxyethyl acrylate and polyacrylamide. These polymers may be copolymers as long as hydrophilicity is not impaired.
These may be used alone or in combination of two or more.
The amount used is from 20% by weight to 99% by weight, preferably from 25% by weight to 95% by weight, more preferably from 30% by weight to 90% by weight, based on the total solid weight of the hydrophilic layer.

In the present invention, the organic hydrophilic polymer can be crosslinked with a known crosslinking agent. Known crosslinking agents include polyfunctional isocyanate compounds, polyfunctional epoxy compounds, polyfunctional amine compounds, polyol compounds, polyfunctional carboxyl compounds, aldehyde compounds,
Polyfunctional (meth) acrylic compound, polyfunctional vinyl compound,
Polyfunctional mercapto compounds, polyvalent metal salt compounds, polyalkoxysilane compounds and their hydrolysates, polyalkoxytitanium compounds and their hydrolysates, polyalkoxyaluminum compounds and their hydrolysates, polymethylol compounds, polyalkoxymethyl compounds, etc. It is also possible to add a known reaction catalyst to promote the reaction. The amount used is 1% by weight to 50% by weight, preferably 3% by weight to 40% by weight, more preferably 5% by weight to 35% by weight, based on the total solid content in the coating solution of the hydrophilic layer. .

The system capable of sol-gel conversion which can be used for the formation of the inorganic hydrophilic matrix of the hydrophilic layer of the present invention has a network structure in which a bonding group derived from a polyvalent element has an oxygen atom via an oxygen atom. At the same time, the polyvalent metal also has an unbonded hydroxyl group or alkoxy group, and is a polymer having a resin-like structure in which these are mixed. In some cases, the network-like resin structure becomes strong as the ether bonding proceeds. In addition, it also has a function of modifying the surface of the solid fine particles by binding a part of the hydroxyl groups to the solid fine particles and changing the degree of hydrophilicity. The polyvalent bonding element of the compound having a hydroxyl group or an alkoxy group that undergoes sol-gel conversion is aluminum, silicon, titanium, zirconium, or the like, and any of these can be used in the present invention. A sol-gel conversion system using a siloxane bond will be described. aluminum,
The sol-gel conversion using titanium and zirconium can be performed by substituting silicon for each element described below.

That is, particularly preferably used are:
This is a system containing a silane compound having at least one silanol group and capable of sol-gel conversion. Hereinafter, a system utilizing the sol-gel conversion will be further described. The inorganic hydrophilic matrix formed by the sol-gel conversion is preferably a resin having a siloxane bond and a silanol group. During the elapse of time, the hydrolysis-condensation of the silanol group proceeds to form the structure of the siloxane skeleton, which is formed by the progress of gelation. Further, in the matrix of this gel structure, for the purpose of improving physical properties such as film strength and flexibility, improving coating properties, adjusting hydrophilicity, etc.
It is also possible to add the above-mentioned organic hydrophilic polymer and crosslinking agent.

The siloxane resin forming the gel structure is represented by the following general formula (I), and the silane compound having at least one silanol group is obtained by hydrolysis of the silane compound represented by the following general formula (II). It is not always necessary to obtain a partially hydrolyzed product of the silane compound of the general formula (II) alone. It may be a mixed composition.

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The siloxane resin represented by the general formula (I) is
It is formed by sol-gel conversion of at least one compound of the silane compounds represented by the following general formula (II), wherein at least one of R ^{01 to} R ^{03 in} the general formula (I) represents a hydroxyl group, and Represents an organic residue selected from the symbols R ⁰ and Y in the general formula (II).

Formula (II) (R ⁰ ) n Si (Y) _4-n

In the general formula (II), R ⁰ represents a hydroxyl group, a hydrocarbon group or a heterocyclic group. Y represents a hydrogen atom, a halogen atom (representing a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), —OR ¹ , —OCOR ^2, or —N (R ³ )
(R ⁴⁾ represents the (R ^1, R ² each represents a hydrocarbon group,
R ³ and R ⁴ may be the same or different and represent a hydrogen atom or a hydrocarbon group), and n represents 0, 1, 2 or 3.

The hydrocarbon group or heterocyclic group represented by R ^{0 in} the general formula (II) is, for example, a linear or branched alkyl group having 1 to 12 carbon atoms which may be substituted (for example, methyl group , Ethyl group, propyl group, butyl group, pentyl group,
A hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group and the like; the groups substituted by these groups include a halogen atom (a chlorine atom, a fluorine atom, a bromine atom), a hydroxy group, a thiol group, and a carboxy group. Group, sulfo group, cyano group, epoxy group, -OR 'group (R' is a methyl group, an ethyl group, a propyl group, a butyl group, a heptyl group,
Hexyl, octyl, decyl, propenyl, butenyl, hexenyl, octenyl, 2-hydroxyethyl, 3-chloropropyl, 2-cyanoethyl, N, N-dimethylaminoethyl, 1-bromoethyl Group, 2- (2-methoxyethyl) oxyethyl group, 2
-Methoxycarbonylethyl group, 3-carboxypropyl group, benzyl group, etc.), -OCOR "group (R"
Represents the same content as R ′), —COOR ″
Group, -COR "group, -N (R"")(R"") group (R""
Represents the same content as a hydrogen atom or the aforementioned R ′, and may be the same or different), —NHCONHR ″ group, —
NHCOOR "group, -Si (R") ₃ group, -CONH
R ′ ″ group, —NHCOR ″ group and the like. These substituents may be substituted plurally in the alkyl group),

A linear or branched alkenyl group having 2 to 12 carbon atoms which may be substituted (for example, vinyl, propenyl, butenyl, pentenyl, hexenyl, octenyl, decenyl, dodecenyl and the like) And the groups substituted with these groups include those having the same contents as the groups substituted with the above-mentioned alkyl groups), having 7 to 14 carbon atoms.
Optionally substituted aralkyl groups (for example, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, etc .; Groups having the same content as the group to be mentioned, or may be substituted plurally),

An optionally substituted alicyclic group having 5 to 10 carbon atoms (for example, cyclopentyl, cyclohexyl, 2
-Cyclohexylethyl group, 2-cyclopentylethyl group, norbornyl group, adamantyl group and the like, the group substituted with these groups include those having the same contents as the substituents of the alkyl group, and those substituted with a plurality of May be substituted), an aryl group having 6 to 12 carbon atoms which may be substituted (for example,
A phenyl group, a naphthyl group, and examples of the substituent include those having the same contents as the group substituted with the alkyl group, and a plurality of the groups may be substituted), or a nitrogen atom, an oxygen atom,
A condensable heterocyclic group containing at least one atom selected from sulfur atoms (for example, the heterocyclic ring includes a pyran ring, a furan ring, a thiophene ring, a morpholine ring, a pyrrole ring, a thiazole ring, and an oxazole And a ring, a pyridine ring, a piperidine ring, a pyrrolidone ring, a benzothiazole ring, a benzoxazole ring, a quinoline ring, a tetrahydrofuran ring, etc., which may contain a substituent. The same content may be mentioned, or a plurality of the same may be substituted).

In the general formula (II), -OR ¹ group of Y, -OC
As a substituent of the OR ² group or the —N (R ³ ) (R ⁴ ) group,
For example, it represents the following substituents. —OR ¹ group includes R ¹
Is an aliphatic group having 1 to 10 carbon atoms which may be substituted (for example, methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, pentyl group, octyl group, nonyl group, decyl group, propenyl group) , Butenyl, heptenyl, hexenyl, octenyl, decenyl, 2-hydroxyethyl, 2-hydroxypropyl, 2-methoxyethyl, 2- (methoxyethyloxo) ethyl, 1- (N, N -Diethylamino) ethyl group, 2-methoxypropyl group, 2-cyanoethyl group, 3-methyloxapropyl group, 2-chloroethyl group, cyclohexyl group, cyclopentyl group, cyclooctyl group, chlorocyclohexyl group, methoxycyclohexyl group, benzyl group, Phenethyl group, dimethoxybenzyl group, methylbenzyl group, bromobenzyl It represents a group and the like).

In the —OCOR ² group, R ² is an aliphatic group having the same content as R ¹ or an aromatic group having 6 to 12 carbon atoms which may be substituted (the aromatic group is an aryl group in the aforementioned R). And the same as those exemplified for the group).
In the —N (R ³ ) (R ⁴ ) group, R ³ and R ⁴ may be the same or different from each other, and each may be a hydrogen atom or an optionally substituted aliphatic group having 1 to 10 carbon atoms ( For example, those having the same contents as those of R ¹ in the above-mentioned —OR ¹ group can be mentioned). More preferably, the total number of carbon atoms of R ³ and R ⁴ 16
It is within the number. Specific examples of the silane compound represented by the general formula (II) include, but are not limited to, the following.

Tetrachlorosilane, tetrabromosilane, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetra-n-propylsilane, tetra-t-butoxysilane, tetra-n-butoxysilane, dimethoxydiethoxysilane, methyltrichlorosilane , Methyltribromosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltri-t-butoxysilane, ethyltrichlorosilane, ethyltribromosilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriiso Propoxysilane, ethyltri-t-butoxysilane, n-propyltrichlorosilane, n-propyltribromosilane, n-propyltrimethoxysilane,
n-propyltriethoxysilane, n-propyltriisopropoxysilane, n-propyltri-t-butoxysilane, n-hexyltrichlorosilane, n-hexyltribromosilane, n-hexyltrimethoxysilane, n
-Hexyltriethoxysilane,

N-hexyltriisopropoxysilane,
n-hexyltri-t-butoxysilane, n-decyltrichlorosilane, n-decyltribromosilane, n-decyltrimethoxysilane, n-decyltriethoxysilane, n-decyltriisopropoxysilane, n-decyltrit-butoxysilane , N-octadecyltrichlorosilane, n-octadecyltribromosilane, n-octadecyltrimethoxysilane, n-octadecyltriethoxysilane, n-octadecyltriisopropoxysilane, n-octadecyltri-t-butoxysilane, phenyltrichlorosilane, phenyl Tribromosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, phenyltri-t-butoxysilane, dimethyldichlorosilane, dimethyldibromosilane, Methyldimethoxysilane, dimethyldiethoxysilane, diphenyl dichlorosilane, diphenyl bromine, diphenyldimethoxysilane,
Diphenyldiethoxysilane, phenylmethyldichlorosilane, phenylmethyldibromosilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane,

Triethoxyhydrosilane, tribromohydrosilane, trimethoxyhydrosilane, isopropoxyhydrosilane, tri-t-butoxyhydrosilane, vinyltrichlorosilane, vinyltribromosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, Vinyl tri-t-butoxysilane, trifluoropropyltrichlorosilane, trifluoropropyltribromosilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, trifluoropropyltriisopropoxysilane, trifluoropropyltri-t-butoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxip Pills trimethoxysilane, gamma
-Glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriisopropoxysilane, γ-glycidoxypropyltri-t-butoxysilane, γ-methacryloxypropylmethyldimethoxysilane,

Γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriisopropoxysilane, γ-methacryloxypropyltri-t-butoxysilane, γ-aminopropylmethyldimethoxysilane , Γ-aminopropylmethyldiethoxysilane, γ-
Aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropyltri-t-butoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane,
γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyltriisopropoxysilane, γ-mercaptopropyltri-t-butoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β-
(3,4-epoxycyclohexyl) ethyltriethoxysilane and the like.

Along with the silane compound represented by the general formula (II) used for forming the inorganic hydrophilic matrix of the hydrophilic layer according to the present invention, the silane compound binds to the resin during the sol-gel conversion of Ti, Zn, Sn, Zr, Al, etc. And a metal compound capable of forming a film. Examples of the metal compound used include Ti (OR ⁵ ) ₄ (R ⁵ is a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, etc.), Ti
Cl ₄ , Ti (CH ₃ COCHCOCH ₃ ) ₂ (OR ⁵ ) ₂ ,
Zn (OR ⁵ ) ₂ , Zn (CH ₃ COCHCOCH ₃ ) ₂ ,
Sn (OR ⁵ ) ₄ , Sn (CH ₃ COCHCOCH ₃ ) ₄ ,
Sn (OCOR ⁵ ) ₄ , SnCl ₄ , Zr (OR ⁵ ) ₄ , Z
r (CH ₃ COCHCOCH ₃ ) ₄ , Al (OR ⁵ ) ₃ , A
1 (CH ₃ COCHCOCH ₃ ) _{3 and the} like.

Further, in order to promote the hydrolysis and polycondensation reaction of the silane compound represented by the general formula (II), and the metal compound used in combination, it is preferable to use an acidic catalyst or a basic catalyst in combination. As the catalyst, an acid or basic compound used as it is or in a state of being dissolved in a solvent such as water or alcohol (hereinafter referred to as an acidic catalyst or a basic catalyst, respectively) is used. The concentration at that time is not particularly limited, but when the concentration is high, hydrolysis /
The polycondensation rate tends to increase. However, when a basic catalyst having a high concentration is used, a precipitate may be formed in the sol solution. Therefore, the concentration of the basic catalyst is desirably 1 N (concentration conversion in an aqueous solution) or less.

The type of the acidic catalyst or the basic catalyst is not particularly limited. Specific examples of the acidic catalyst include hydrogen halides such as hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, hydrogen sulfide, perchloric acid, and hydrogen peroxide. Examples of basic catalysts include ammonia, carboxylic acids such as carbonic acid, formic acid and acetic acid, substituted carboxylic acids in which R of the structural formula represented by RCOOH is substituted with another element or a substituent, and sulfonic acids such as benzenesulfonic acid. Examples include ammoniacal bases such as water and amines such as ethylamine and aniline. For further details of the above sol-gel method, see Sakuhana Saio, "Sol-gel Method Science", Agne Shofusha Co., Ltd. (1988),
Hiroshi Hirashima, "Functional thin film production technology by the latest sol-gel method"
It is described in detail in books such as the General Technology Center (published) (1992).

In the hydrophilic layer of the organic or inorganic hydrophilic matrix of the present invention, in addition to the above, control of the degree of hydrophilicity, improvement of the physical strength of the hydrophilic layer, and mutual Various kinds of compounds can be added, such as an improvement in dispersibility, an improvement in applicability and an improvement in printability. For example, plasticizers, pigments, dyes, surfactants, hydrophilic particles and the like can be mentioned. The hydrophilic particles are not particularly limited, but preferably include silica, alumina, titanium oxide, magnesium oxide, magnesium carbonate, calcium alginate and the like. These can be used for promoting hydrophilicity, strengthening a film, and the like. More preferably,
It is silica, alumina, titanium oxide or a mixture thereof. In a preferred embodiment, the hydrophilic layer of the organic or inorganic hydrophilic matrix of the present invention particularly contains metal oxide particles such as silica, alumina, and titanium oxide.

Silica has many hydroxyl groups on the surface and the inside constitutes a siloxane bond (—Si—O—Si—). In the present invention, silica that can be preferably used is ultrafine silica particles having a particle diameter of 1 to 100 nm, also referred to as colloidal silica, dispersed in water or a polar solvent. Specifically, it is described in "Applied Technology of High Purity Silica", Vol. 3, supervised by Yoshitoshi Kaga and Ei Hayashi, CMC Corporation (1991).

The alumina which can be preferably used is an alumina hydrate (boehmite type) having a colloidal size of 5 to 200 nm and an anion (for example, a halogen ion such as a fluorine ion or a chlorine ion) in water. , A carboxylate anion such as an acetate ion) as a stabilizer. The titanium oxide that can be preferably used has an average primary particle size of 50 to 500.
nm anatase or rutile titanium oxide,
If necessary, it is dispersed in water or a polar solvent using a dispersant.

In the present invention, the average primary particle diameter of the hydrophilic particles which can be preferably used is 1 to 5000 nm.
And more preferably 10 to 1000 nm.
In the hydrophilic layer of the present invention, these hydrophilic particles may be used alone or in combination of two or more. The amount used is based on the total solid weight of the hydrophilic layer.
It is 5% to 90% by weight, preferably 10% to 70% by weight, more preferably 20% to 60% by weight.

The hydrophilic layer of the organic or inorganic hydrophilic matrix used in the present invention may be dissolved or dispersed in a suitable solvent such as water or a polar solvent such as methanol or ethanol alone or in a mixed solvent thereof. Is applied, dried and cured on a support. The coating weight is preferably 0.1 to 5 g / m ² , preferably 0.1 to 5 g / m ² , after drying.
It is 3 to 3 g / m ² , more preferably 0.5 to ² g / m ² . The coating weight of the hydrophilic layer after drying was 0.1 g / m ^2.
If it is too low, the retention of a hydrophilic liquid such as a fountain solution or the like, or an undesirable result such as a decrease in the film strength is given. give.

The thin film of metal or metal compound having a hydrophilic surface used in the hydrophilic layer of the present invention is not particularly limited as long as it has a surface hydrophilic property. Tellurium, titanium,
Iron, cobalt, nickel, indium, bismuth, zirconium, zinc, lead, vanadium, silicon, copper, silver metals and alloys and metal oxides corresponding to each metal,
Metal carbide, metal nitride, metal boride, metal sulfide,
Metal halides. Substantially, the surface of the thin film of the metal and the metal compound is in a highly oxidized state, and works advantageously in terms of hydrophilicity. Therefore, a thin film of a metal oxide such as indium tin oxide, tungsten oxide, manganese oxide, silicon oxide, titanium oxide, aluminum oxide, and zirconium oxide can be suitably used as the hydrophilic layer of the present invention.

For forming a thin film of a metal or a metal compound having a hydrophilic surface used in the hydrophilic layer of the present invention, a PVD method such as a vacuum evaporation method, a sputtering method, and an ion plating method may be used.
Method D (physical vapor deposition) or CVD (chemical vapor deposition) is used as appropriate. For example, in a vacuum evaporation method, resistance heating, high-period induction heating, electron beam heating, or the like can be used as a heating method. In addition, oxygen, nitrogen, or the like may be introduced as a reactive gas, or reactive vapor deposition using means such as ozone addition or ion assist may be used.

When a sputtering method is used, a pure metal or a target metal compound can be used as a target material. When a pure metal is used, oxygen, nitrogen or the like is introduced as a reactive gas. DC power supply,
A pulse DC power supply or a high-frequency power supply can be used.

Prior to the formation of a thin film by the above method, degassing of the substrate by heating the substrate or vacuum glow treatment on the surface of the heat-sensitive layer may be performed to improve the adhesion to the heat-sensitive layer. For example, in vacuum glow processing, 1 to 10 mt
A high frequency is applied to the base under a pressure of about orr to form a glow discharge, and the substrate can be processed by the generated plasma. Further, the effect can be improved by increasing the applied voltage or introducing a reactive gas such as oxygen or nitrogen.

The thickness of the metal or metal compound thin film having a hydrophilic surface used for the hydrophilic layer of the present invention is 10 nm to 3 nm.
000 nm is preferred. More preferably, 20 to 150
0 nm. If the thickness is too small, undesired results such as a decrease in retention of a hydrophilic liquid such as a fountain solution and a decrease in film strength are given. The hydrophilic layer of the present invention may be formed by layering hydrophilic layers having the same composition or different compositions.

In the present invention, a hydrophilic protective layer may be provided on the hydrophilic layer for the purpose of protecting the surface hydrophilicity of the hydrophilic layer. The hydrophilic protective layer is preferably easily removed with water or fountain solution. For example, modified polyvinyl alcohol such as polyvinyl alcohol (polyvinyl acetate having a saponification degree of 60% or more), carboxy-modified polyvinyl alcohol, starch, Its derivatives,
Carboxymethylcellulose and its salts, cellulose derivatives such as hydroxyethylcellulose, casein, gelatin, acacia, polyvinylpyrrolidone,
Provided by applying and drying a water-soluble polymer solution such as vinyl acetate-crotonic acid copolymer, styrene-maleic acid copolymer, polyacrylic acid and its salt, polymethacrylic acid and its salt, polyethylene glycol and polyethyleneimine. be able to. The dry weight of the hydrophilic protective layer in this case is preferably 0.01-5 g / m ^2, more preferably 0.05 to 2 g / m ^2.

(Oleophobic layer) The oleophobic layer in the present invention is a layer having an ink-repellent surface. A conventionally known ink repellent surface can be used. Fluorine or a silicone compound is well known as a substance having a low surface energy on conventionally known ink repellent surfaces. In particular, silicone rubber (silicone elastomer) is suitably used for the ink repellent layer of the waterless plate. Silicone rubbers are broadly classified into three types: condensation type silicone rubbers, addition type silicone rubbers, and radiation-curable silicone rubbers. Various known silicone rubbers can be used. The condensation type silicone rubber layer is a film formed by curing the following composition A.

Composition A (a) 100 parts by weight of diorganopolysiloxane (b) 3 to 70 parts by weight of condensation type crosslinking agent (c) 0.01 to 40 parts by weight of catalyst

The diorganopolysiloxane of the component (a) is a polymer having a repeating unit represented by the following general formula, wherein 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, 60% or more of R ¹ and R ² are a methyl group or a vinyl halide group,
Those such as halogenated phenyl groups are preferred.

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It is preferable to use such a diorganopolysiloxane having hydroxyl groups at both ends. The component (a) has a number average molecular weight of 3,000 to 1
000, more preferably 10,000 to
70,000. Component (b) may be of any type as long as it is of the condensation type, but is preferably one represented by the following general formula.

R ¹ m · Si · Xn

(M + n = 4, n is 2 or more)

Here, R ¹ has the same meaning as R ¹ described above, and X is a substituent as shown below. · Cl, Br, a halogen such as I, · H or ^{OH, OCOR 3, OR 3,} -O-N = C (R 4)
^{(R 5), - N (} R 4) (R 5) organic substituent such as.

Here, 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. Component (c) is tin, zinc,
Known catalysts such as metal carboxylate salts of lead, calcium, manganese and the like, for example, dibutyltin laurate, lead octylate, lead naphthenate and the like, and chloroplatinic acid and the like can be mentioned. The addition type silicone rubber layer is a film formed by curing the following composition B.

Composition B (d) 100 parts by weight of diorganopolysiloxane having an addition-reactive functional group (e) 0.1 to 25 parts by weight of organohydrogenpolysiloxane (f) 0.00001 to 1 part by weight of addition catalyst

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 the organic group other than the alkenyl group is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or an aryl group. The component (d) may optionally have a small amount of a hydroxyl group. Component (d) is a number average molecular weight of 3,000
~ 100,000, more preferably 10,000
0 to 70,000.

As the component (e), polydimethylsiloxane having hydrogen groups at both terminals, α, ω-dimethylpolysiloxane, (methylsiloxane) (dimethylsiloxane) copolymer having methyl groups at both terminals, cyclic polymethylsiloxane, Examples thereof include a polymethylsiloxane having a terminal trimethylsilyl group, and a dimethylsiloxane having both terminal trimethylsilyl groups) (methylsiloxane) copolymer.

The component (f) is arbitrarily selected from known compounds, and is particularly preferably a platinum-based compound, such as platinum alone, platinum chloride, chloroplatinic acid, and olefin-coordinated platinum. In order to control the curing rate of these compositions, organopolysiloxanes containing vinyl groups such as tetracyclo (methylvinyl) siloxane, alcohols containing carbon-carbon triple bonds, acetone, methyl ethyl ketone, methanol, ethanol, propylene glycol It is also possible to add a crosslinking inhibitor such as monomethyl ether.

The radiation-curable silicone rubber layer is
A film formed by curing a silicone base polymer having a functional group capable of being polymerized by irradiation with a radiation by a crosslinking reaction. The coating solution is a solution obtained by dissolving the base polymer together with an initiator. Is formed. In general, crosslinking is generated by irradiation with ultraviolet rays using a base polymer having an acrylic functional group. About these silicone rubbers, "R
& D Report No. 22 Latest Application Technology of Silicone "
(Published by CMC, 1982), Japanese Patent Publication No. 56-23150
And JP-A-3-15553 and JP-B-5-1934.

The oleophobic layer may have a seal, if necessary.
Fine powder of inorganic substances such as lica, calcium carbonate, titanium oxide
Powder, silane coupling agent, titanate coupling
Aids such as adhesives and aluminum coupling agents and light
A polymerization initiator may be added. The above system used in the present invention
The composition of the silicone rubber layer includes, for example, petroleum solvents,
Sopar E, Isopar G, Isopar H (Esso Chemical
Products), hexane, heptane, toluene, xylene, etc.
Solvents alone or in appropriate combinations of these solvents
Dissolve in a medium, apply on the substrate, dry, cure and set
Is also good. The silicone rubber layer in the present invention, after drying
If the coating weight is small, the ink repellency decreases and scratches may occur.
If there are problems such as panning and the applied weight after drying is large
In this case, the coating weight after drying is
0.5 to 5 g / m ^TwoIs preferred, more preferably
Is 1-3 g / m^TwoIt is.

Further, various silicone rubber layers may be further coated on the silicone rubber layer. Furthermore, for the surface protection of the silicone rubber layer, a transparent film such as polyethylene, polypropylene,
Polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyethylene terephthalate, cellophane, etc. may be laminated or a polymer coating may be applied. These films may be used after being stretched. Further, the surface may be subjected to a matting process, but one having no matting process is preferable in the present invention.

(Laser Exposure) In the present invention, the laser light energy used for recording is absorbed in the heat-sensitive layer of the lithographic printing plate precursor of the present invention and converted into heat energy. Due to chemical reactions or physical changes such as combustion, melting, decomposition, vaporization, and explosion of a part or the whole, the adhesion between the heat-sensitive layer and the upper layer is reduced. In the present invention, a laser beam is used to expose the lithographic printing plate precursor. The laser used is
There is no particular limitation as long as it provides an exposure amount necessary to cause a sufficient decrease in adhesion to remove the hydrophilic layer or the oleophobic layer, which is the upper layer of the heat-sensitive layer. Ar laser, carbon dioxide laser Gas lasers, solid-state lasers such as YAG lasers, and semiconductor lasers can be used. Usually, a laser having a power of 50 mW class or more is required.

From the viewpoints of practicality such as maintainability and price, semiconductor lasers and semiconductor-pumped solid-state lasers (YAG
Laser) is preferably used. The recording wavelength of these lasers is in the infrared wavelength region, and an oscillation wavelength of 800 nm to 1100 nm is often used. Also,
When a film for protecting the surface of the hydrophilic layer or the oleophobic layer is provided, the film may be exposed as it is, or may be exposed after peeling, as long as the film is transparent to the laser beam used. .

(Development Treatment) The lithographic printing plate precursor of the present invention, which has been exposed by the above method, is subjected to a development treatment to remove the hydrophilic layer or the oleophobic layer of the laser-exposed portion having reduced adhesion to the lower layer. You. In the present invention, it is required that the developing process is performed within 120 seconds after the image exposure by the laser. The development processing of the present invention includes, for example, applying pressure to the surface of the exposed lithographic printing plate precursor, in the presence or absence of a processing solution, using a cloth, a rubber blade, a rubbing member such as a pad or a brush, and the like. Is carried out by rubbing. Thereby, the hydrophilic layer or the oleophobic layer in the laser image area is removed, and the area becomes the ink receiving area. In consideration of the removability of the hydrophilic layer or the oleophobic layer of the laser exposed part and the cleaning property of the scum from the plate surface, in the absence of the processing liquid, after performing the rubbing treatment, in the presence of the processing liquid, Further, it is also preferable to perform a rubbing treatment.

As the processing liquid used in the present invention, those known as processing liquids for lithographic printing plates can be used. Known examples include, for example, aliphatic hydrocarbons (hexane, heptane, “Isoper E, H, G” (manufactured by Esso Chemical Co., Ltd.) or gasoline, kerosene, etc.), and aromatic hydrocarbons (toluene, xylene Etc.), halogenated hydrocarbons (trichlene, etc.), those obtained by adding the following polar solvents to the above-mentioned hydrocarbon solvents, and polar solvents themselves.

Examples of the polar solvent include alcohols (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 (acetone, methyl ethyl ketone, etc.), esters (ethyl acetate, methyl lactate, butyl lactate, propylene glycol monomethyl) Ether acetate, diethylene glycol acetate Diethyl phthalate) and others (triethyl phosphate, tricresyl phosphate and the like). In addition, water is added to the organic solvent-based developer, the organic solvent is solubilized in water using a surfactant or the like, and an alkali agent (for example, sodium carbonate, diethanolamine, Sodium, etc.), water (tap water, pure water, distilled water, etc.) or an aqueous solution of a surfactant.

Among them, from the viewpoints of safety and flammability, water or an aqueous solution containing water as a main component is preferable, and the concentration of the solvent is desirably less than 40% by weight. Particularly preferred is an aqueous solution of a surfactant (anionic, nonionic, cationic, etc.). The temperature of the treatment liquid can be any temperature, but is preferably from 10C to 50C. The above laser exposure and rub development processing are described in Japanese Patent No. 293.
No. 8398, Japanese Patent No. 2648081, US Pat.
No. 158, EP 887204A, GB2297719
In a printing machine (CTC type printing machine) equipped with an imaging laser unit and a plate surface cleaning unit described in No. A or the like, it can be carried out after mounting a lithographic printing plate precursor on a printing machine cylinder. Further, the rub development process and the subsequent washing and drying processes are described in JP-A-2-200.
No. 61, it can also be performed by an automatic processor. When the printing plates developed as described above are stacked and stored, it is preferable to insert and insert a slip sheet to protect the printing plates.

[0101]

EXAMPLES The present invention will be described in more detail with reference to Examples. However, the present invention is not limited to the following examples. Example 1 [Production of support] Thickness 180 with corona treatment on both sides
The following coating solution was applied to one surface of a polyethylene terephthalate having a thickness of μm, and heated and dried (180 ° C., 30 seconds) to form an intermediate layer having a dry coating amount of 0.2 g / m ² .

(Intermediate Layer Coating Solution) Polyester latex (Pesthresin A-520, 8 g, manufactured by Takamatsu Oil & Fat Co., Ltd., solid content 30% by weight) Melamine compound (Sumitec Resin M-3, 6 g Sumitomo Chemical Co., Ltd.) ), Active ingredient concentration: 80% by weight) Colloidal silica (Snowtex C, 4.8 g, manufactured by Nissan Chemical Co., Ltd.) Surfactant (polyoxyethylene alkylphenyl ether, 0.7 g Emulgen 911 Kao Corporation) Polystyrene (Nipol UFN1008, 0.04 g, manufactured by Nippon Zeon Co., Ltd., solid content 20% by weight) Distilled water 81 g

Next, the following coating solution was applied on the surface opposite to the intermediate layer, and dried by heating (180 ° C., 30 seconds) to form a back layer having a dry coating amount of 0.2 g / m ² .

(Back Layer Coating Solution) Acrylic resin aqueous dispersion (Dulima ET-410, 10 g, manufactured by Nippon Pure Chemical Co., Ltd., solid content: 20% by weight) Tin oxide-antimony oxide aqueous dispersion 90 g (average particle size) : 0.1 μm, 17% by weight) Melamine compound (Sumitec Resin M-3, 0.2 g, manufactured by Sumitomo Chemical Co., Ltd., active ingredient concentration: 80% by weight) Alkyl sulfonate sodium salt aqueous solution 0.6 g (Sanded BL) (Manufactured by Sanyo Chemical Industry Co., Ltd., 44% by weight) 45 g of distilled water

Further, the following coating solution was applied on the back layer and dried by heating (170 ° C., 30 seconds) to form a protective layer having a dry coating amount of 0.05 g / m ² , thereby producing a support.

(Coating Solution for Protective Layer) Polyolefin latex (Chemipearl S-120, 6.2 g, manufactured by Mitsui Chemicals, Inc., solid content: 27% by weight) Colloidal silica (Snowtex C, manufactured by Nissan Chemical Co., Ltd.) 2 g aqueous solution of sodium alkylsulfonate 0.6 g (Sanded BL, manufactured by Sanyo Chemical Industries, Ltd., 44% by weight) Epoxy compound (Denacol EX-614B, 0.6 g, manufactured by Nagase Kasei Co., Ltd., active ingredient concentration: 100% by weight %) 90 g of distilled water

[Formation of heat-sensitive layer] The following mixed solution was stirred with glass beads for 30 minutes using a paint shaker to disperse carbon black, and the glass beads were filtered off. The fluorine-based surfactant Megafac F177 (Dainippon) 0.005 g of Ink Chemical Industry Co., Ltd.)
A heat-sensitive layer coating solution was prepared. This coating solution was applied onto the intermediate layer so as to have a dry coating amount of 1.0 g / m ^2, and was dried by heating (80 ° C., 2 minutes) to form a heat-sensitive layer.

(Coating solution for heat-sensitive layer) Polyurethane resin 3.0 g (4 mol of 2,4-tolylene diisocyanate / 1 mol of 1,3-butylene glycol / 2 mol of 2,2′-dimethylolpropanoic acid / 1,2-) Carbon black (MA600, manufactured by Mitsubishi Chemical Corporation, 1.5 g DBP oil absorption 131 ml / 100 g) Dispersant (SOLSPERS S24000R, manufactured by ICI) 0.2 g propylene glycol monomethyl ether 40 g methyl ethyl ketone 60 g

[Formation of oleophobic layer] The following coating solution was applied on the heat-sensitive layer, heated and dried (110 ° C, 1 minute) to obtain an addition type silicone having a dry coating amount of 2.0 g / m ^2. A rubber layer was formed to obtain a waterless lithographic printing plate precursor.

(Coating solution for oleophobic layer) α, ω-divinylpolydimethylsiloxane (degree of polymerization: 1500) 9.0 g (CH ₃ ) ₃ SiO (SiH (CH ₃ ) O) ₈ -Si (CH ₃ ) ₃₀ 2g olefin - chloroplatinic acid 0.1g controlling agent _{[HC≡CC (CH 3) 2 -O} -Si (CH 3) 3] 0.2g Isopar (manufactured by Exxon chemical (Co.)) E 120 g

The obtained lithographic printing plate precursor of the present invention without water
And Presstek plate setter PEARL
setter (wavelength 830 nm, beam diameter 28 μm (1
/ E ^Two), Equipped with a semiconductor laser with a maximum output of 750mW)
175 lpi (1270 dpi) dot image formation
Was done. Next, within 15 seconds after the end of the image exposure, the current
Image processing was performed. The developing treatment includes a processing solution 1 having the following composition.
This is done by rubbing the plate surface with the
The silicone rubber layer in the exposed area was removed. as a result,
Sharp reproduction of dot area ratio from 2% to 98%
Waterless lithographic printing plate with edge silicone image shaped
Was made.

(Treatment liquid 1) Polyoxyethylene sorbitan monooleate 5 g (Reodol TW-O106, manufactured by Kao Corporation) Anti-scale agent BK2 (manufactured by Fuji Photo Film Co., Ltd.) 2 g Water 993 g

Further, printing is performed using the waterless lithographic printing plate thus formed (printing machine: Diamond IF manufactured by Mitsubishi Heavy Industries, Ltd.).
2. Ink: Aqualess Echo New M black, manufactured by Toyo Ink Co., Ltd .; cooling of the ink-applying roller: 20 ° C.).

Example 2 The waterless planographic printing plate precursor of Example 1 was processed into a roll form, attached to a Heidelberg CTC type four-color printing machine Quick Master DI46-4plus, and automatically lasered under standard conditions. Performed image exposure and development processing (using a genuine Quickmaster cleaning liquid for the processing liquid), and printing (inks of AQUALES ECHONEW M manufactured by Toyo Ink Co., Ltd.) Each used). At this time, the developing process was started within 15 seconds after the image exposure. As a result, a good full-color printed matter without missing of the image portion due to poor development was obtained.

Example 3 As carbon black, Denka black (powder) (manufactured by Denki Kagaku Kogyo KK, DBP oil absorption 115 ml / 100)
A waterless planographic printing plate precursor was formed in exactly the same manner as in Example 1 except that g) was used. Next, when image exposure and processing were performed in the same manner as in Example 1, the dot area ratio was 2%.
A waterless lithographic printing plate was formed having a sharp edge silicone image with up to 98% reproduction. Further, when printing was carried out in the same manner as in Example 1 using the formed lithographic printing plate without water, a good printed matter was obtained in which the image portion was not lost due to poor development.

Example 4 As carbon black, # 20 (manufactured by Mitsubishi Chemical Corporation)
DBP oil absorption 121ml / 100g)
When image exposure, development processing, and printing were performed in the same manner as in Example 3, the same results as in Example 3 were obtained. Example 5 MA230 was used as carbon black by Mitsubishi Chemical Corporation.
Image exposure, development processing, and printing were performed in the same manner as in Example 3 except that the amount of DBP oil absorption was 113 ml / 100 g), and the same results as in Example 3 were obtained. Example 6 An image was exposed, developed, and printed in the same manner as in Example 3 except that # 3230B (manufactured by Mitsubishi Chemical Corporation, DBP oil absorption 140 ml / 100 g) was used as the carbon black. The same result as in Example 3 was obtained.

Example 7 As carbon black, # 3750 (Mitsubishi Chemical Corporation)
Image exposure, development, and printing were performed in the same manner as in Example 3, except that the amount of DBP oil absorption was 210 ml / 100 g), and the same results as in Example 3 were obtained. Example 8 Toka Black # 5500 as carbon black
(Tokai Carbon Co., Ltd., DBP oil absorption 155ml / 1
Image exposure, development processing, and printing were performed in the same manner as in Example 3 except that 00g) was used, and the same results as in Example 3 were obtained. Example 9 Toka Black # 4500 as carbon black
(Tokai Carbon Co., Ltd., DBP oil absorption 168ml / 1
Image exposure, development processing, and printing were performed in the same manner as in Example 3 except that 00g) was used, and the same results as in Example 3 were obtained.

Example 10 An image was exposed, developed and printed in the same manner as in Example 3 except that STERLING V (manufactured by Cabot Corporation, DBP oil absorption: 91 ml / 100 g) was used as carbon black. The same result as in Example 3 was obtained. Examples 11 to 18 Except for using the waterless planographic printing plate precursors of Examples 3 to 10 as the waterless planographic printing plate precursor, image exposure, development processing and printing were performed in the same manner as in Example 2. However, the same results as in Example 2 were obtained.

Comparative Example 1 As carbon black, MA11 (Mitsubishi Chemical Corporation)
A waterless lithographic printing plate precursor was formed in exactly the same manner as in Example 1 except that DBP oil absorption was 64 ml / 100 g). Next, when image exposure and processing were performed in the same manner as in Example 1, only a dot area ratio of 4% to 95% could be reproduced, and the edge portion of the silicone image was not sharp but had a shape in which fringes remained. Was. Further, when printing was performed in the same manner as in Example 1 using the formed waterless planographic printing plate, omission of an image portion due to poor development occurred, and dot density became uneven due to dot shape variation. ,
Good prints could not be obtained.

Comparative Example 2 The waterless planographic printing plate precursor of Comparative Example 1 was processed into a roll form, and in the same manner as in Example 2, a CTC type 4-color printing machine Quickmaster DI46-4pl manufactured by Heidelberg.
US, image exposure, development processing and printing were performed. could not.

Examples 19 to 22 The time from the image exposure until the start of the development processing was set as follows.
Image exposure, development, and printing were performed in the same manner as in Example 2 except that the time was changed to 30, 60, 90, and 120 seconds, and the same results as in Example 2 were obtained. Comparative Examples 3 to 6 After the image exposure, the time until the start of the development processing was
Image exposure, development processing, and printing were performed in the same manner as in Comparative Example 2 except that the time was changed to 30 seconds, 60 seconds, 90 seconds, and 120 seconds. The non-uniform dot density due to missing portions and uneven dot shape was improved, but the same good printed matter as in Example 2 could not be obtained.

Example 23 A lithographic printing plate precursor with water was formed in exactly the same manner as in Example 1 except that the following hydrophilic layer was formed instead of the silicone rubber layer. (Formation of hydrophilic layer) The following coating solution was applied on the heat-sensitive layer of Example 1 and dried by heating (100 ° C, 10 minutes) to form a hydrophilic layer having a dry weight of 2 g / m ^2. did.

(Hydrophilic layer coating liquid) 20 g of titanium oxide 20% / polyvinyl alcohol 2% aqueous dispersion 20 g (titanium oxide (manufactured by Wako Pure Chemical Industries, Ltd., rutile type, average particle size 200 nm)) / PVA117 (Kuraray Co., Ltd. )) = 10/1 weight ratio) Methanol silica (manufactured by Nissan Chemical Co., Ltd .: 5 g Colloid consisting of a methanol solution containing 30% by weight of 10 nm to 20 nm silica particles) Sol gel preparation liquid (the following composition) 4.5 g Polyoxy Ethylene nonyl phenyl ether 0.025 g (Nonipol 100, manufactured by Sanyo Chemical Industries, Ltd.) Water 15 g Methanol 5 g

(Preparation of Sol-Gel Preparation Solution) A solution having the following composition was aged at room temperature for 1 hour to prepare a sol-gel preparation solution.

8.5 g of tetraethoxysilane, 1.8 g of methanol, 15.0 g of water, 0.015 g of phosphoric acid

Next, image exposure and processing were performed in the same manner as in Example 1. As a result, lithographic printing with water having a sharp edge image of the hydrophilic layer with a dot area ratio of 2% to 98% was reproduced. A plate was formed. Further, printing was performed using the formed lithographic printing plate with water (printing machine: SOR-M manufactured by Heidelberg, dampening solution: EU-3 (manufactured by Fuji Photo Film Co., Ltd.)) at 1% by volume and isopropanol at 10% by volume.
Aqueous solution and ink added: Dainippon Ink and Chemicals, Inc.
GEOS-G black), a good printed matter without an image portion missing due to poor development was obtained.

Example 24 The same procedures as in Example 2 were carried out except that the lithographic printing plate precursor with water of Example 23 was processed into a roll form and mounted, and monochrome printing was performed using an emulsion ink having the following composition. When image exposure, development processing, and printing were performed, a good printed matter without an image portion missing due to poor development was obtained.

(Emulsion ink composition) [Preparation of emulsion ink] (1) Preparation of varnish (hereinafter referred to as "varnish")
Parts indicate parts by weight. )

Varnish A: Maleated petroleum resin (Neopolymer 120: Nippon Oil Co., Ltd.) 47 parts Spindle oil 53 parts Gel varnish B: Rosin-modified phenol resin (Tamanol 354: Arakawa Chemical Industries, Ltd.) 34 parts Machine Oil 31 parts Spindle oil 31 parts Aluminum stearate 4 parts Varnish C: Gilsonite 25 parts Machine oil 75 parts

(2) Preparation of oil-based ink component:

Carbon black 14 parts Calcium carbonate (Shiraisha DD: manufactured by Shiraishi Industry Co., Ltd.) 5 parts Varnish A 27 parts Gel varnish B 7 parts Varnish C 11 parts Flax oil 4 parts Machine oil 6 parts Spindle oil 24 parts Cyanine blue One copy

(3) Preparation of hydrophilic component:

Purified water 5 parts Ethylene glycol 25 parts Propylene glycol 35 parts Glycerin 34 parts Surfactant (polyoxyethylene alkyl phenyl ether, 1 part Liponox NCE: manufactured by Lion Fat & Oil Co., Ltd.)

100 parts by weight of the oil-based ink component of (2) and 70 parts by weight of the hydrophilic component of (3) were mixed by stirring.
An O-type emulsion ink was prepared.

Example 25 A waterless planographic printing plate precursor was formed in exactly the same manner as in Example 1 except that a condensation type silicone rubber layer was formed using the following coating solution. Next, the obtained waterless planographic printing plate precursor was subjected to image exposure, development processing, and printing in the same manner as in Example 2, and the same results as in Example 2 were obtained.

(Composition of Silicone Rubber Layer Coating Solution) Dimethylpolysiloxane having hydroxyl groups at both ends 9.00 g (degree of polymerization 700) Methyltriacetoxysilane 0.3 g Dibutyltin dioctaate 0.2 g Isopar G (Esso Chemical Co., Ltd. 160 g)

[0137]

According to the method for forming a lithographic printing plate of the present invention, the lithographic printing plate precursor is subjected to image exposure by laser light,
Even if development processing is performed within a short time, a lithographic printing plate can be formed without deterioration in developability.

Claims (1)

[Claims] 1. A lithographic printing plate precursor comprising: a support, a heat-sensitive layer containing carbon black and a binder polymer; and a hydrophilic layer or an oleophobic layer on the heat-sensitive layer. In a method for forming a lithographic printing plate by performing a development treatment within 120 seconds after performing imagewise laser exposure to remove the hydrophilic layer or the oleophobic layer in the laser exposed portion, Dibutyl phthalate (DBP) oil absorption of carbon black is 90 ml
/ 100 g or more, a method of forming a lithographic printing plate.