JP2003019871A - Original plate for direct drawing printing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an original plate for direct drawing printing capable of printing many printed matters of a clear image having no lack, no strain or the like of the image without scumming as an offset original plate. SOLUTION: The original plate for direct drawing printing comprises an image acceptive layer on a water-resisting support. The image acceptive layer contains a resin containing needle-like particles each having a ruggedness on a surface and a bond in which a metal atom and/or semi-metal atom are connected via oxygen atom, and at least a binding resin made of a composite of the resin and an organic polymer having a group capable of forming a hydrogen bond.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a direct drawing type lithographic printing plate precursor, and more particularly to a lithographic printing plate precursor for providing a lithographic printing plate capable of printing a large number of printed matters having clear images without background stains. .

[0002]

2. Description of the Related Art At present, lithographic printing plates used mainly in the field of light printing include (1) a water-resistant support,
Direct drawing type original plate provided with a hydrophilic image receiving layer, (2) Direct drawing plate making on an original plate provided with an image receiving layer (lipophilic) containing zinc oxide on a water resistant support, and then a non-image area To obtain a printing plate by desensitizing treatment with a desensitizing treatment liquid, (3) An electrophotographic photosensitive material having a photoconductive layer containing photoconductive zinc oxide on a water-resistant support as an original plate , The non-image part after image formation,
Examples include a printing plate which is desensitized with a desensitizing solution, and (4) a silver salt photographic type original plate in which a silver halide emulsion layer is provided on a water-resistant support.

With the recent development of office equipment and the development of office automation, in the printing field, various methods such as electrophotographic printers, thermal transfer printers, ink jet printers and the like can be used for the direct drawing type lithographic printing plate precursor (1). There is a demand for an offset lithographic printing method in which plate making (that is, image formation) is performed, and a printing plate is directly created without performing a specific process for forming a printing plate.

A conventional direct drawing type lithographic printing plate precursor is provided with a surface layer serving as an image receiving layer on both sides of a support such as paper via a back layer and an intermediate layer. PV or back layer
It is composed of a water-soluble resin such as A and starch, a water-dispersible resin such as a synthetic resin emulsion, and a pigment. The image receiving layer is usually composed of an inorganic pigment, a water-soluble resin and a waterproofing agent.

Examples of the inorganic pigment include kaolin, clay, talc, calcium carbonate, silica, titanium oxide, zinc oxide, barium sulfate and alumina.

As the water-soluble resin, polyvinyl alcohol (PVA), modified PVA such as carboxy PVA,
Starch and its derivatives, carboxymethyl cellulose, cellulose derivatives such as hydroxyethyl cellulose,
Water-soluble resins such as casein, gelatin, polyvinylpyrrolidone, vinyl acetate-crotonic acid copolymer, and styrene-maleic acid copolymer are mentioned.

Further, glyoxal is used as a water resistance agent,
Examples thereof include aminoplast initial condensates such as melamine formaldehyde resins and urea formaldehyde resins, modified polyamide resins such as methylolated polyamide resins, polyamide / polyamine / epichlorohydrin adducts, polyamide epichlorohydrin resins, and modified polyamide polyimide resins.

In addition, it is also known that ammonium chloride and a crosslinking catalyst for a silane coupling agent can be used in combination.

Further, as a binder used in the image receiving layer of the direct-drawing type lithographic printing plate precursor, it has a functional group capable of generating a carboxyl group, a hydroxyl group, a thiol group, an amino group, a sulfo group or a phosphono group when decomposed. , A resin containing a functional group that is cured by heat / light and previously cross-linked is used (Japanese Patent Laid-Open Nos. 1-226395 and 1-269593,
JP-A-1-288488), the functional group-containing resin and the heat / photocurable resin are used in combination (Japanese Patent Laid-Open No. 1-266546).
No. 1-275191, No. 1-309068), and the functional group-containing resin in combination with a crosslinking agent (JP-A 1-267093, 1-271292, 1-3).
No. 09067), improvement of hydrophilicity of non-image area, improvement of film strength of image receiving layer, and further improvement of printing durability have been investigated.

Further, in the image receiving layer, resin particles having a fine particle diameter of 1 μm or less containing a hydrophilic group such as a carboxyl group, a sulfo group and a phosphono group are contained together with an inorganic pigment and a binder (Japanese Patent Laid-Open No. Hei 9 (1999) -29100). 4-201387, 4-2
No. 23196), or fine resin particles containing a functional group that produces a hydrophilic group as described above by decomposition (Japanese Patent Laid-Open Nos. 4-319491 and 4-353).
No. 495, No. 5-119545, No. 5-58071
JP-A-5-69684) to improve the hydrophilicity of the non-image area.

However, in the conventional printing plate thus obtained, the hydrophobicity is increased by increasing the addition amount of the waterproofing agent or using the hydrophobic resin in order to improve the printing durability. However, there is a problem that the printing durability is improved, but the hydrophilicity is reduced to cause printing stains. On the other hand, when the hydrophilicity is improved, the water resistance is deteriorated and the printing durability is deteriorated.

In particular, under a use environment at a high temperature of 30 ° C. or higher, the surface layer is dissolved in the immersion water used for offset printing, and there are drawbacks such as deterioration of printing durability and occurrence of printing stains. Furthermore, in the case of a direct-drawing type lithographic printing plate precursor, an oil-based ink or the like is drawn as an image portion on the image receiving layer, and if the adhesion between the receiving layer of the printing plate and the oil-based ink is not good,
Even if the non-image area has sufficient hydrophilicity and the above-mentioned printing stains do not occur, the oil-based ink in the image area is lost during printing, resulting in a decrease in printing durability. It has not reached the point where it is resolved to.

On the other hand, a plate comprising a hydrophilic layer containing titanium oxide, polyvinyl alcohol and hydrolyzed tetramethoxysilane or tetraethoxysilane as an image receiving layer (JP-A-3-42679, 10-268583).
No., etc.). However, when the plate was actually made and printed as a printing plate, the printing durability of the image was insufficient.

[0014]

SUMMARY OF THE INVENTION The present invention solves the above problems of the conventional direct drawing type lithographic printing plate precursor.

An object of the present invention is to provide an excellent direct drawing type lithographic printing original plate which does not generate spot stains as well as uniform stain stains on the entire surface as an offset printing plate.

Another object of the present invention is to provide a direct-drawing lithographic printing plate precursor which provides a printing plate capable of printing a large number of clear image printed matter having no background stains and no image defects or distortions. That is.

[0017]

The above object can be achieved by the following constitutions. (1) In a direct-drawing type lithographic printing plate precursor having an image receiving layer on a water-resistant support, needle-shaped particles having irregularities on the surface, and metal atoms and / or semimetal atoms are oxygen atoms in the image receiving layer. Direct-drawing lithographic printing, characterized in that it contains at least a binder resin composed of a resin containing a bond connected via a bond and an organic polymer containing a group capable of forming a hydrogen bond with the resin. Original edition. (2) The direct drawing type lithographic printing plate precursor as described in (1) above, wherein the acicular particles have an average diameter of 0.01 to 3 μm and an average length of 1 to 100 μm. (3) The aspect ratio (average length / average diameter) of the acicular particles is 10 to 5,000.
The direct-drawing lithographic printing plate precursor as described in (1) or (2). (4) The acicular particles having irregularities on the surface are metal compound particles having photocatalytic properties, in which minute particles of a metal substance are carried on the surface, and the acicular particles are any of the above (1) to (3). Direct drawing type lithographic printing plate precursor. (5) Microparticles of a metal substance carried on the surface of a metal compound particle having photocatalytic properties irradiate the metal compound particle with active light in the presence of a metal salt of the metal element having a smaller ionization tendency than hydrogen element. The direct-drawing lithographic printing plate precursor as described in (4) above, which is a minute piece of the metal element deposited on the surface.

The preferred embodiments of the present invention will be described below. (6) The metal compound particles having photocatalytic properties are TiO ₂ , R
TiO ₃ (R is an alkaline earth metal atom), AB _2-x C _x D
_{3-x Ex} O ₁₀ (A is hydrogen atom or alkali metal atom, B is alkaline earth metal atom or lead atom, C is rare earth atom, D
Is a metal atom belonging to Group 5A element of the periodic table, E is a metal atom belonging to Group 4 element of the periodic table, x is an arbitrary value from 0 to 2), SnO ₂ , ZrO ₂ , ZnO, Bi ₂ O ₃ , W
O ₃ , Fe ₂ O ₃ , Cu ₂ O, V ₂ O ₅ , MoO ₃ , Al
₂ O ₃ , Cr ₂ O ₃ , ZnS, MoS ₂ , FeS, CuS,
At least one of PbS, MoSe ₂ , PbSe, CuSe and SiC
The direct drawing type lithographic printing plate precursor as described in (4) or (5). (7) The resin containing a bond in which a metal atom and / or a semimetal atom is connected via an oxygen atom is a polymer obtained by hydrolysis co-condensation of at least one compound represented by the following general formula (I). (1) to (6), characterized by
The lithographic printing plate precursor for direct drawing described in any of 1. Formula (I) (R ⁰ ) _n M ⁰ (Y) _zn [In the formula (I), R ⁰ represents a hydrogen atom, a hydrocarbon group or a heterocyclic group, Y represents a reactive group, and M ⁰ Is 3-6
Represents a valent metal or metalloid, z represents the valence of M ⁰ , and n represents ⁰ , 1, 2, 3 or 4. However, z−n is 2 or more. ] (8) The smoothness of the image receiving layer surface is 30 (s
ec / 10 mL) or more above (1)-
The direct-drawing lithographic printing plate precursor as described in any of (7). (9) In a direct drawing type lithographic printing plate precursor having an image receiving layer on a water-resistant support, in the image receiving layer, a metal salt of a metal element having a smaller ionization tendency than hydrogen element, and a metal compound particle having photocatalytic property And a resin containing a bond in which a metal atom and / or a semimetal atom are connected via an oxygen atom,
A direct-drawing lithographic printing plate precursor comprising at least a binder resin composed of a composite of the resin and an organic polymer having a group capable of forming a hydrogen bond.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.

In the present invention, the resin having a particle having irregularities on the surface, a resin containing a bond in which a metal atom and / or a semimetal atom are connected via an oxygen atom, and a group capable of forming a hydrogen bond with the resin are contained. When combined with a binder resin composed of a composite with an organic polymer, the interaction of each material is high,
By improving the dispersibility of particles having unevenness on the surface, a film having excellent printing durability can be obtained after plate making, and at the same time, the particle surface has fine unevenness, so that the image can be fixed by heat fixing. Printing durability is further improved by melting the resin component and adhering to the irregularities to develop an anchor effect. Also,
Due to the fine mesh shape formed by the acicular particles, the manifestation of the anchor effect becomes more remarkable, and the printing durability is further improved. Further, when the amount of water retention on the surface of the image receiving layer during printing is sufficiently maintained, good image adhesion and hydrophilicity can be exhibited.

The particles having irregularities on the surface provided for the image receiving layer of the present invention will be described.

Examples of particles having surface irregularities (hereinafter also referred to as surface irregular particles) include particles obtained by fixing small particles to the surface of needle-shaped core particles.

Here, the acicular core particles constituting the surface-roughened particles may be inorganic particles or organic particles and are not particularly limited.

The inorganic acicular particles include metals, oxides, complex oxides, hydroxides, carbonates, sulfates, silicates, phosphates, nitrides, carbides, sulfides and at least 2 of these.
Examples of the compound such as one or more kinds, specifically, silica,
Glass, titanium oxide, zinc oxide, alumina, zircon oxide, tin oxide, potassium titanate, aluminum borate, magnesium oxide, magnesium borate, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, basic magnesium sulfate, calcium carbonate, carbonic acid magnesium,
Calcium sulfate, magnesium sulfate, calcium silicate, magnesium silicate, calcium phosphate, silicon nitride, titanium nitride, aluminum nitride, silicon carbide, titanium carbide,
Examples thereof include zinc carbide and a complex compound of at least two of these. Preferably, silica, glass, titanium oxide, alumina, conductive titanium oxide (tin oxide doped), potassium titanate, aluminum borate, magnesium oxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium phosphate, calcium sulfate. Etc.

Examples of the organic needle-like particles include carbon compounds, polymer whiskers, celluloses, and composites of at least one of these with an inorganic compound.
Graphite, carbon nanotube, polyoxymethylene whiskers, aromatic polyester whiskers, aramid whiskers, cellulose acetate, ethyl cellulose,
Microbial cellulose and the like can be mentioned. Preferred are graphite, poly (p-oxybenzoyl) whiskers, poly (2-oxy-6-naphthoyl) whiskers, microbial cellulose and the like.

The size of the acicular particles is preferably 3 μm or less in average diameter and 100 μm or less in average length, more preferably 0.01 to 3 μm in average diameter, 1 to 100 μm in average length, and further preferably. Has an average diameter of 0.02
μm, average length 1 to 50 μm. The aspect ratio (average length / average diameter) of the acicular particles is 5 to 10,000.
About 0 is suitable, preferably about 10 to 5,000, more preferably about 20 to 2,500. When the content is within these ranges, the effects of the present invention described above are effectively exhibited.

In the present invention, it is not necessary that all the particles used are acicular particles, and the amount of acicular particles is 2 times the total particle amount.
It is preferably 5% by mass or more, more preferably 50% by mass or more, and further preferably 75% by mass or more based on the total amount of particles.

Particles that can be used in combination with the above-mentioned acicular particles may be inorganic particles or organic particles and are not particularly limited. Examples of the inorganic particles include metal powders, metal oxides, metal nitrides, metal sulfides, metal carbides and their composites, and the like, preferably metal oxides and metal sulfides, and more preferably Is glass, SiO ₂ , TiO ₂ ,
Examples thereof include particles of ZnO, Fe ₂ O ₃ , ZrO ₂ , SnO ₂ , ZnS, CuS and the like. Examples of the organic particles include synthetic resin particles and natural polymer particles, preferably acrylic resin,
Polyethylene, polypropylene, polyethylene oxide, polypropylene oxide, polyethyleneimine,
Polystyrene, polyurethane, polyurea, polyester, polyamide, polyimide, carboxymethylcellulose, gelatin, starch, chitin, chitosan and the like, more preferably, resin particles of acrylic resin, polyethylene, polypropylene, polystyrene and the like.

The average particle size of the particles which can be used in combination with the above-mentioned acicular particles is suitably 0.03 to 10 μm, preferably 0.05 to 8 μm, and more preferably 0.08 to 5 μm. Is.

Inorganic particles are mainly used as the small particles that can be fixed to the needle-shaped core particles to form particles having irregularities on the surface. For example, metal powders, metal oxides, metal nitrides and composites thereof and the like can be mentioned, preferably metal oxides and the like, more preferably metal, glass, SiO ₂ , TiO ₂ , ZnO, Fe ₂ O. ₃ , ZrO ₂ , Sn
These are particles such as O ₂ .

The average particle size of the small particles is suitably 0.005 to 3 μm, preferably 0.01 to 2 μm, more preferably 0.01 to 1 μm.

In the surface-roughened particles, the average particle size of the small particles is suitably 1/3 or less of the average diameter of the core particles, preferably 1/5 or less, more preferably 1/10 or less.

The degree of coverage of the small particles adhered to the surface of the core particles can be arbitrarily selected within the range where the effects of the present invention are exhibited. Generally, the coverage is 2% or more, and the entire surface may be coated. In order to obtain excellent printing durability, the coverage is preferably 5 to 90%, more preferably 10 to 60%.
Is.

The surface-roughened particles of the present invention can be obtained, for example, by a method utilizing hetero-aggregation described in “New Development of Fine Particle Polymer” edited by Toray Research Center Co., Ltd., a method by a polymerization reaction from the surface of core particles, and powder processing. It can be easily produced by a dry coagulation stirring method using a hybridizer described in “Particle Design Engineering” edited by the Society. In addition, some kinds of surface uneven particles can be produced by depositing small particles on the surface of the core particles.

Specific examples of the method utilizing hetero-aggregation include a method in which fine particles having different surface charges are mixed with and adsorbed to the core particles, and fine particles having a functional group that reacts with the surface of the core particles are dissolved in the solution. Examples include a method of mixing and adsorbing in the inside. Preferably, a method of mixing oxide particles such as anionic SiO ₂ and TiO ₂ having a surface as a core particle and an alumina sol having a surface cationic in an aqueous solution, and a core particle having a surface having a cationic alumina particle and a surface anion are mixed. Examples of the method include mixing colloidal silica, titania and the like in an aqueous solution.

As a method of the polymerization reaction from the surface of the core particle, specifically, the core particle surface has an alkoxysilyl group, and the silica sol-gel reaction grows from the alkoxysilyl group on the surface of the core particle to form fine particles. Methods and the like.

As a dry coagulation stirring method using a hybridizer, specifically, resin particles (acrylic resin, polyester, polyethylene, etc.) having a heat fusion property on the surface of the core particles are dry mixed by a hybridizer. There is a method.

The content of the surface irregularity particles in the image receiving layer is preferably 10 to 95% by mass, more preferably 20.
Is about 90% by mass.

According to one embodiment of the present invention, the surface-roughened particles are photocatalytic metal compound particles (corresponding to core particles) having fine particles (corresponding to small particles) of a metal substance carried on the surface.
Consists of.

The metal compound particles having a photocatalytic property are those which carry on their surface a metal substance which is activated by the absorption of the irradiated active light and is present in the vicinity. Specifically, TiO ₂ , RTiO ₃ (R is an alkaline earth metal atom), AB _2-x C _x D _3-x E _x O ₁₀ (A is a hydrogen atom or an alkali metal atom, B is an alkaline earth metal atom or a lead atom, and C is a rare earth metal. Atom, D is a metal atom belonging to Group 5A element of the Periodic Table, E is a metal atom belonging to Group 4 element of the Periodic Table, x is an arbitrary value from 0 to 2), SnO ₂ , Zr
O ₂ , ZnO, Bi ₂ O ₃ , WO ₃ , Fe ₂ O ₃ , Cu ₂ O,
V ₂ O ₅ , MoO ₃ , Al ₂ O ₃ , Cr ₂ O ₃ , ZnS, Mo
S ₂ , FeS, CuS, PbS, MoSe ₂ , PbSe,
CuSe, SiC, etc. can be mentioned.

Titanium oxide (TiO ₂ ) can be prepared by any known method such as calcination of ilmenite or titanium slag with sulfuric acid by heating, or chlorination by heating followed by oxygen oxidation. Although any crystalline form of titanium oxide can be used, anatase type is particularly preferred because of its high sensitivity. It is well known that anatase type crystals can be obtained by selecting firing conditions in the process of firing titanium oxide. In that case, amorphous titanium oxide or rutile-type titanium oxide may coexist, but the anatase-type crystal is 40%.
The above content, preferably 60% or more, is preferable for the above reason.

R of RTiO ₃ is a metal atom belonging to the alkaline earth elements of the periodic table such as magnesium, calcium, strontium, barium and beryllium, and strontium and barium are particularly preferable. Two or more kinds of alkaline earth metal atoms can coexist in the above R as long as the total is stoichiometrically matched with the above formula.

In the compound represented by the general formula AB _2-x C _x D _3-x E _x O ₁₀ , A is a monovalent atom selected from a hydrogen atom and an alkali metal atom such as sodium, potassium, rubidium, cesium and lithium. At least two of these atoms may coexist as long as their sum is stoichiometrically matched to the above formula.

B is an alkaline earth metal atom or a lead atom, and two or more kinds of atoms may coexist as long as they are stoichiometrically matched as described above.

C is a rare earth atom, preferably scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, holmium, europium,
It is an atom belonging to a lanthanoid-based element such as gadolinium, terbium, thulium, ytterbium, and lutetium, and two or more kinds may coexist as long as the total is stoichiometrically matched with the above formula.

D is one or more elements selected from Group 5A elements of the periodic table, and examples thereof include vanadium, niobium and tantalum. Also, as long as the stoichiometric relationship is satisfied, two or more 5A
Group elements may coexist.

E is also silicon, germanium, tin,
It is a metal atom belonging to Group 4 elements such as lead, titanium, and zirconium, and two or more kinds of Group 4 metal atoms may coexist.

X represents an arbitrary numerical value of 0-2.

General formula AB_2-xC_xD_3-xE_xO_TenRepresented by
Specific examples of the compound include CsLa ₂NbTi₂O_Ten, H
Ca_1.5La_0.5Nb_2.5Ti_0.5O_Ten, LaNbTi₂O
_TenAnd so on.

As a method for producing these compounds, for example, CsLa ₂ NbTi ₂ O ₁₀ fine particles are prepared by finely crushing Cs ₂ CO ₃ , La ₂ O ₃ , NbO ₅ and TiO ₂ corresponding to their stoichiometry in a mortar. Then, it is placed in a platinum crucible, baked at 130 ° C. for 5 hours, cooled, placed in a mortar and pulverized into fine particles of several microns or less. This method uses CsLa
Not limited to ₂ NbTi ₂ O ₁₀ type fine particles, HCa _1.5 La _0.5
Nb _2.5 Ti _0.5 O ₁₀ , LaNbTi ₂ O _10, etc.
It applied to the _{B 2-x C x D 3} -x E x O 10 (0 ≦ x ≦ 2).

As other metal compounds having photocatalytic properties, commercially available and easily available compounds can be used.

In the present invention, the above TiO ₂ , RT
iO ₃ , AB _2-x C _x D _3-x E _x O ₁₀ , SnO ₂ , ZrO ₂ ,
ZnO, Bi ₂ O ₃ , WO ₃ , Fe ₂ O ₃ , Cu ₂ O, V
₂ O ₅ , MoO ₃ , Al ₂ O ₃ , Cr ₂ O ₃ , ZnS, Mo
S ₂ , FeS, CuS, PbS, MoSe ₂ , PbSe,
At least one of CuSe and SiC can be dispersed or contained in the image receiving layer alone or in combination of two or more kinds.

The metal substance supported as fine particles on the surface of the metal compound particles having a photocatalytic property is preferably one which exhibits hydrophilicity in the supported state. The metal substance itself may be hydrophilic or hydrophobic, and various known metal substances can be used.

Preferred metallic substances which can be used in the present invention are Al, Si, Ti, V, Cr, Mn, Fe and C.
o, Ni, Cu, Zn, Y, Zr, Mo, Ag, Au,
Examples thereof include Pt, Pd, Rh, In, Sn and W.

These metal substances can be carried on the surface of the metal compound particles having photocatalytic properties by being irradiated with active light while existing in the vicinity of the metal compound particles having photocatalytic properties. Preferably, water-soluble salts of these metal substances are used, and the metal compound particles having photocatalytic properties are irradiated with active light in the presence of the water-soluble salts, whereby the water-soluble salts are photoreduced to form fine particles. This is a method of depositing on the surface of metal compound particles having photocatalytic properties.

The image receiving layer formed by dispersing the photocatalytic metal compound particles having the minute particles of the metal substance supported on the surface in the binder resin can be easily produced. Specifically, a method for forming an image receiving layer by mixing metal compound particles having photocatalytic properties, in which minute pieces of a metal substance are supported on the surface, with an binder resin, in an aqueous solution of a metal salt corresponding to the metal of the minute pieces. In, the method of irradiating with an active light by immersing the image receiving layer containing dispersed metal compound particles having photocatalytic properties, an aqueous solution of a metal salt is impregnated into the image receiving layer containing metal compound particles having photocatalytic properties. Any method such as a method of irradiating with active light and a method of irradiating with an active light an image receiving layer containing a metal salt together with metal compound particles having photocatalytic properties may be used. When an aqueous solution of a metal salt is used, the concentration of the metal salt in the aqueous solution is 0.0001 to 10 mol / L, preferably 0.001 to 5 mol / L, more preferably 0.
It is used at a concentration of 01 to 3 mol / L. When a metal salt is impregnated or added to the image receiving layer, the concentration in the coating layer is 1 × 10 ⁻⁷ to 1 × 10 ⁻² mol / m ² , preferably 1 × 10 ⁻⁶ or more on a dry film basis. It is impregnated or added in an amount of 5 × 10 ⁻³ mol / m ² , more preferably 1 × 10 ^{−5 to} 3 × 10 ⁻³ mol / m ² .

Among the metals constituting these metal micro-pieces, particularly preferable are metals (weaker) having an ionization tendency smaller than that of hydrogen element, that is, Cu, Hg, Ag, Pt and A.
u, Pd and Rh, particularly preferred metals are Cu and A
g and Au.

The water-soluble metal salt used for forming the metal fine pieces is a nitrate, sulfate, halogenate, halide salt, halogenic acid complex salt, or ammonia complex salt of the above-mentioned metals (ammoniacal aqueous solution of each of the above salts). And sulfite.

The active light refers to light having a wavelength at which a compound having a photocatalytic property is activated by light absorption to exhibit a catalytic function. Active light sources include mercury lamps such as high-pressure mercury lamps, xenon arc lamps, xenon discharge lamps, various fluorescent lamps, tungsten lamps, halogen lamps, and laser light having an oscillation wavelength in the visible or ultraviolet region. To be used depending on the type of compound having

Further, upon irradiation with actinic light, a photocatalytically oxidizable compound may be further present for the purpose of promoting the deposition of metal fine particles. Compounds used for this purpose have sugar groups such as maltose, lactose, dextran, dextrin and soluble starch, and carbohydrates, aldehydes such as formaldehyde, acetaldehyde, gluoxal, succindialdehyde, and hydroxyl groups such as sorbitol, polyethylene glycol and hydroquinone. Alcohols and phenols, compounds having a carboxyl group such as polyacrylic acid, ethers such as ethylene glycol dimethyl ether, amides such as N-methylpyrrolidone, esters such as ethylene glycol monomethyl monoacetate, ketones such as acetylacetone. And the like. When used, the addition amount varies depending on the kind of the compound, but is 0.1 to 50% by weight, preferably 0.5 to 30% by weight of the solid weight of the image receiving layer.
% By weight.

In order to exert the effect of the present invention,
In addition to the photocatalytic property of the metal compound, the image receiving layer containing the metal compound also has a level of light absorption, that is, a particle density, required for the light conversion effect to occur effectively. Is desirable. Sufficient light absorption capacity
It is to have a spectral absorption region with an absorbance of 0.3 or more in the spectral wavelength region of 300 to 1200 nm that can be converted into light. Specifically, the wavelength region of irradiation light (in the case of single wavelength light, the wavelength is Has a maximum absorption of 0.3 or more in a wavelength range of 100 nm centered on or, or has a continuous absorption of 0.3 or more even if it has no absorption maximum in this wavelength range.
This means that there is an absorption wavelength region of 00 nm or more. If the condition of the light absorption capacity is satisfied, the hydrophilicity and the image adhesion of the plate material are improved by performing the exposure at the wavelength corresponding to this absorption wavelength range.

Next, the binder resin used in the image receiving layer of the present invention will be described. The binder resin of the present invention includes a resin containing a bond in which a metal atom and / or a semimetal atom are connected via an oxygen atom (hereinafter, simply referred to as “(semi) metal-containing resin”), The resin is a composite of a resin and an organic polymer containing a group capable of forming a hydrogen bond. The “composite of (semi) metal-containing resin and organic polymer” is used to mean a sol-like substance and a gel-like substance.

The (semi) metal-containing resin means a polymer mainly containing a bond composed of "oxygen atom-metal atom or semimetal atom-oxygen atom". Here, the (semi) metal-containing resin may contain both a metal atom and a semimetal atom. Preferred are resins containing only semi-metal atoms and resins containing semi-metal atoms and metal atoms.

The (semi) metal-containing resin has the following general formula (I):
It is preferably a polymer obtained by hydrolysis-cocondensation of a compound represented by Formula (I) (R ⁰ ) _n M ⁰ (Y) _zn [In the formula (I), R ⁰ represents a hydrogen atom, a hydrocarbon group or a heterocyclic group, Y represents a reactive group, and M ⁰ Is 3-6
Represents a valent metal or metalloid, z represents the valence of M ⁰ , and n
Represents 0, 1, 2, 3, or 4. However, z-n is 2
That is all. Here, the hydrolytic cocondensation is a reaction in which a reactive group repeats hydrolysis and condensation under acidic or basic conditions to polymerize. The above compounds are used singly or in combination of two or more kinds to produce a (semi) metal-containing resin.

Next, the compound represented by formula (I) will be described in detail. R ⁰ in the general formula (I) is preferably a linear or branched alkyl group having 1 to 12 carbon atoms which may be substituted (eg, methyl group, ethyl group, propyl group, butyl group, pentyl. Groups, hexyl groups, heptyl groups, octyl groups, nonyl groups, decyl groups, dodecyl groups, etc .; groups that can be substituted by these groups include halogen atoms (chlorine atom, fluorine atom, bromine atom), hydroxy group, thiol group , Carboxy group, sulfo group, cyano group,
Epoxy group, -OR 'group (R' is a hydrocarbon group such as methyl group, ethyl group, propyl group, butyl group, hexyl group, heptyl group, octyl group, decyl group, propenyl group, butenyl group, hexenyl group , An octenyl group, 2-
Hydroxyethyl group, 3-chloropropyl group, 2-cyanoethyl group, N, N-dimethylaminoethyl group, 2-bromoethyl group, 2- (2-methoxyethyl) oxyethyl group, 2-methoxycarbonylethyl group, 3-carboxy Propyl group, benzyl group, etc.), -OCOR '
Group, -COOR 'group, -COR' group, -N (R ")
(R ") (R" represents a hydrogen atom or the same content as R'and may be the same or different), -NHCON
HR 'group, -NHCOOR' group, -Si (R ') ₃ group,
Examples thereof include a -CONHR "group and a -NHCOR 'group.
Multiple of these substituents may be substituted in the alkyl group)},

An optionally substituted linear or branched alkenyl group having 2 to 12 carbon atoms (for example, vinyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, octenyl group, decenyl group, dodecenyl group, etc. Examples of the group substituted with these groups include those having the same contents as the group substituted with the alkyl group, and a plurality of them may be substituted), or a group having 7 to 14 carbon atoms may be substituted. Good aralkyl group (eg, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, etc.); the group substituted by these groups is the same as the group substituted by the alkyl group. The contents of
A plurality of them may be substituted), and an alicyclic group having 5 to 10 carbon atoms which may be substituted (for example, cyclopentyl group, cyclohexyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl group, norbonyl group, adamantyl group) etc,
Examples of the group substituted with these groups include those having the same contents as the above-mentioned substituents of the alkyl group, and a plurality of them may be substituted), and an optionally substituted aryl group having 6 to 12 carbon atoms ( For example, a phenyl group and a naphthyl group, examples of the substituent include those having the same content as the group substituted by the alkyl group, and a plurality of them may be substituted),

Alternatively, a heterocyclic group which may be condensed with at least one atom selected from a nitrogen atom, an oxygen atom and a sulfur atom (for example, a hetero ring may be a pyran ring, a furan ring, a thiophene ring or morpholine). A ring, a pyrrole ring, a thiazole ring, an oxazole ring, a pyridine ring, a piperidine ring, a pyrrolidone ring, a benzothiazole ring, a benzoxazole ring, a quinoline ring, a tetrahydrofuran ring and the like, which may have a substituent, may be contained. The same contents as the substituents in the alkyl group are mentioned, and a plurality of them may be substituted).

The reactive group Y is preferably a hydroxy group, a halogen atom (representing a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), a —OR ¹ group, a —OCOR ² group, a —OR group.
^{CH (COR 3) (COR 4} ) group, -CH (COR ³⁾
It represents a (COOR ⁴⁾ groups, or ^{-N (R 5) (R 6} ) group.

In the --OR ¹ group, R ¹ has 1 to 10 carbon atoms.
Optionally substituted aliphatic group (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, propenyl group, butenyl group, heptenyl group) , Hexenyl group, octenyl group, decenyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 2-methoxyethyl group, 2- (methoxyethyloxy) ethyl group, 2-
(N, N-diethylamino) ethyl group, 2-methoxypropyl group, 2-cyanoethyl group, 3-methyloxypropyl group, 2-chloroethyl group, cyclohexyl group, cyclopentyl group, cyclooctyl group, chlorocyclohexyl group, methoxycyclohexyl group , Benzyl group, phenethyl group, dimethoxybenzyl group, methylbenzyl group, bromobenzyl group and the like).

In the —OCOR ² group, R ² is an aliphatic group similar to R ¹ or an aromatic group having 6 to 12 carbon atoms which may be substituted (as the aromatic group, the aryl group in R ⁰ above). The same as those exemplified above can be mentioned). -CH
(COR ³⁾ (COR ⁴⁾ group and the -CH (COR ³⁾ (C
In the OOR ⁴ ) group, R ³ is an alkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, etc.) or aryl group (eg, phenyl group, tolyl group,
Represents a xylyl), R ⁴ represents an alkyl group (e.g. having 1 to 6 carbon atoms, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, etc.), an aralkyl group having 7 to 12 carbon atoms ( For example, benzyl group, phenethyl group, phenylpropyl group, methylbenzyl group, methoxybenzyl group, carboxybenzyl group, chlorobenzyl group, etc. or aryl group (eg, phenyl group, tolyl group, xylyl group, mesityl group, methoxyphenyl group) , Chlorophenyl group, carboxyphenyl group, diethoxyphenyl group, etc.)
Represents Further, in the group —N (R ⁵ ) (R ⁶ ), R ⁵ and R ^{6 are}
May be the same as or different from each other, and each is preferably a hydrogen atom or an optionally substituted aliphatic group having 1 to 10 carbon atoms (for example, those having the same content as R ^{1 of the} aforementioned —OR ¹ group). Can be mentioned). More preferably, the total number of carbon atoms of R ⁵ and R ⁶ is 12 or less.

M ⁰ is preferably a transition metal, a rare earth metal, a metal of Group III to V of the periodic table, or a semimetal.
More preferred are Al, Si, Sn, Ge, Ti, Zr and the like, and further preferred are Al, Si, Sn, Ti,
Zr etc. are mentioned. Si is particularly preferable.

Specific examples of the compound represented by the general formula (I) include, but are not limited to, the followings.

Methyltrichlorosilane, methyltribromosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltri-t-butoxysilane, ethyltrichlorosilane, ethyltribromosilane, ethyltrimethoxysilane, ethyltrimethoxysilane. Ethoxysilane, ethyltriisopropoxysilane, 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-decyltri-t
-Butoxysilane, n-octadecyltrichlorosilane, n-octadecyltribromosilane, n-octadecyltrimethoxysilane, n-octadecyltriethoxysilane, n-octadecyltriisopropoxysilane, n-octadecyltrit-butoxysilane, phenyltrichloro Silane, phenyltribromosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, phenyltri-t-butoxysilane,

Tetrachlorosilane, tetrabromosilane, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, dimethoxydiethoxysilane, dimethyldichlorosilane,
Dimethyldibromosilane, dimethyldimethoxysilane,
Dimethyldiethoxysilane, diphenyldichlorosilane, diphenyldibromosilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenylmethyldichlorosilane, phenylmethyldibromosilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, triethoxyhydrosilane , Tribromohydrosilane, trimethoxyhydrosilane, isopropoxyhydrosilane, tri-t-butoxyhydrosilane, vinyltrichlorosilane, vinyltribromosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltrit-butoxysilane, Trifluoropropyltrichlorosilane, trifluoropropyltribromosilane, trifluoropropyltrimethoxysilane , Trifluoropropyl triethoxysilane, trifluoropropyl triisopropoxysilane, trifluoropropyl tri t- butoxysilane,

Γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-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-aminopropyltrit-butoxysilane, γ-mercaptopropylmethyldimethoxysilane ,
γ-mercaptopropylmethyldiethoxysilane, γ-
Mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyltriisopropoxysilane, γ-mercaptopropyltri-t-butoxinlan, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- ( 3,4
-Epoxycyclohexyl) ethyltriethoxysilane,

Ti (OR) ₄ (R is an alkyl group (for example,
Methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, etc.), TiCl ₄ , Zn (OR)
₂ , Zn (CH ₃ COCHCOCH ₃ ) ₂ , Sn (OR) ₄ ,
_{Sn (CH 3 COCHCOCH 3) 4} , Sn (OCOR) 4,
SnCl ₄ , Zr (OR) ₄ , Zr (CH ₃ COCHCOC
_{H 3) 4, Al (OR} ) 3.

Next, the organic polymer used in the present invention will be described.

The organic polymer used in the present invention is
A group capable of forming a hydrogen bond with a (semi) metal-containing resin (hereinafter,
(Also referred to as a specific bonding group). As such a group, preferably, at least one bond selected from an amide bond (including a carboxylic acid amide bond and a sulfonamide bond), a urethane bond and a ureido bond and a hydroxyl group can be mentioned.

Examples of the organic polymer include those containing, as a repeating unit component, the specific bonding group of the present invention in at least one polymer main chain and / or side chain. Preferably, as the repeating unit component, -N (R ¹¹ ) CO
^{-, - N (R 11)} SO 2 -, - NHCONH- and -N
A component in which at least one bond selected from HCOO- is present in the main chain and / or side chain of the polymer, and / or-
Examples include components containing an OH group. R ¹¹ in the amide bond represents a hydrogen atom or an organic residue, and examples of the organic residue include those having the same contents as the hydrocarbon group and the heterocyclic group for R ⁰ in the general formula (I). .

The polymer main chain contains the specific linking group of the present invention.
As the polymer having, -N (R ¹¹) CO-bonded
Is -N (R¹¹) SO₂-Amide resin having a bond, -N
Ureido resin having HCON-bond, -NHCOO-
Examples thereof include urethane resin containing a bond.

Examples of diamines and dicarboxylic acids or disulfonic acids used for the production of amide resins, diisocyanates used for ureido resins, and diols used for urethane resins include “Polymer Data Handbook-ed. Basic Edition- "Chapter I, Baifukan Co., Ltd. (1
986), Shinzo Yamashita and Tosuke Kaneko, "Handbook of Crosslinking Agents" published by Taiseisha (1981) and the like can be used.

Examples of the other polymer having an amide bond include a polymer containing a repeating unit represented by the following general formula (II), an N-acylated polyalkyleneimine, or polyvinylpyrrolidone and its derivative.

[0083]

[Chemical 1]

In formula (II), Z ¹ represents --CO--, --SO _2-, or --CS--. R ²⁰ has the same content as R ⁰ in formula (I). r ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, etc.). r ¹ may be the same or different. p represents an integer of 2 or 3.

Among the polymers containing the repeating unit represented by the general formula (II), Z ¹ represents -CO- and p is 2
The polymer represented by is obtained by ring-opening polymerization of oxazoline which may have a substituent in the presence of a catalyst. Examples of the catalyst include sulfuric acid esters and sulfonic acid esters such as dimethyl sulfate and p-toluenesulfonic acid alkyl ester; alkyl halides such as alkyl iodide (for example, methyl iodide); metal fluorides of Friedel-Crafts catalysts; Acids such as sulfuric acid, hydrogen iodide and p-toluenesulfonic acid, and oxazolinium salts which are salts of these acids with oxazoline can be used. The polymer may be a homopolymer or a copolymer. Further, it may be a copolymer obtained by grafting this polymer on another polymer.

Specific examples of oxazoline include, for example:
2-oxazoline, 2-methyl-2-oxazoline, 2
-Ethyl-2-oxazoline, 2-propyl-2-oxazoline, 2-isopropyl-2-oxazoline, 2-
Butyl-2-oxazoline, 2-dichloromethyl-2-
Oxazoline, 2-trichloromethyl-2-oxazoline, 2-pentafluoroethyl-2-oxazoline, 2
-Phenyl-2-oxazoline, 2-methoxycarbonylethyl-2-oxazoline, 2- (4-methylphenyl) -2-oxazoline, 2- (4-chlorophenyl)
-2-oxazoline and the like. Preferred oxazolines include 2-oxazoline, 2-methyl-2-oxazoline, 2-ethyl-2-oxazoline and the like. These oxazoline polymers can be used alone or in combination of two or more.

For other polymers having the repeating unit represented by the general formula (II), thiazoline, 4,5-dihydro-1,3-oxazine or 4,5-dihydro-1,3-thiazine may be used instead of oxazoline. Can be similarly obtained by using.

Examples of the N-acylated form of polyalkyleneimine include a -N (CO-R ²⁰ ) -containing carboxylic acid amide obtained by a high molecular reaction with a carboxylic acid halide, or a high-performance compound with a sulfonyl halide. -N obtained by molecular reaction
A sulfonamide compound containing (SO ₂ —R ²⁰ ) — (wherein
R ²⁰ has the same meaning as R ²⁰ in formula (II)) can be mentioned.

Further, the polymer having a specific bonding group of the present invention in the side chain of the polymer contains as a main component a component containing at least one bonding group selected from the specific bonding groups. There are things. Examples of such components include acrylamide, methacrylamide, crotonamide, vinylacetamide, and the following compounds. However, the present invention is not limited to these.

[0090]

[Chemical 2]

[0091]

[Chemical 3]

On the other hand, the hydroxyl group-containing organic polymer may be any of a natural water-soluble polymer, a semi-synthetic water-soluble polymer, and a synthetic polymer. Polymer Compound I ”published by Asakura Shoten (196
0 years), "Development of Comprehensive Technical Data on Water-Soluble Polymers and Water-Dispersible Resins" edited by the Management Development Center, published by Management Development Center Publishing (1981), Shinji Nagatomo, "Applications and Markets of New Water-Soluble Polymers" ( Published by CMC Inc. (1988), "Development of Functional Cellulose" Published by CMC Inc. (1985)
Year)) and so on.

Examples of natural and semi-synthetic polymers include cellulose, cellulose derivatives (cellulose esters; cellulose nitrate, cellulose sulfate, cellulose acetate, cellulose propionate, cellulose succinate, cellulose butyrate, cellulose acetate succinate, acetic acid). Cellulose butyrate, cellulose acetate phthalate, etc., cellulose ethers; methyl cellulose, ethyl cellulose, cyanoethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, ethyl hydroxyethyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl hydroxyethyl cellulose, etc.), starch, starch derivative ( Oxidized starch, esterified starches; nitric acid, sulfuric acid, phosphoric acid, acetic acid, propion , Esterified products of butyric acid, succinic acid, etc., etherified starches; methylated, ethylated, cyanoethylated, hydroxyalkylated, carboxymethylated, etc.), alginic acid, pectin, carrageenan, tamarind gum, natural gums ( Gum arabic, guar gum, locust bean gum, tragacanth gum, xanthan gum, etc.), pullulan, dextran, casein, gelatin, chitin, chitosan and the like.

Examples of synthetic polymers include polyvinyl alcohol, polyalkylene glycols (polyethylene glycol, polypropylene glycol, (ethylene glycol / propylene glycol) copolymers, etc.), allyl alcohol copolymers, and acrylics containing at least one hydroxyl group. Polymer or copolymer of acid ester or methacrylic acid ester (for example, as an ester substituent, 2
-Hydroxyethyl group, 3-hydroxypropyl group,
2,3-dihydroxypropyl group, 3-hydroxy-2
-Hydroxymethyl-2-methylpropyl group, 3-hydroxy-2,2-di (hydroxymethyl) propyl group,
Polyoxyethylene group, polyoxypropylene group,
Etc.), a polymer or copolymer of N-substituted acrylamide or methacrylamide containing at least one hydroxyl group (as the N-substituent, for example, monomethylol group, 2-hydroxyethyl group, 3-hydroxypropyl group) , 1,1-bis (hydroxymethyl) ethyl group, 2,
3,4,5,6-pentahydroxypentyl group, etc.) and the like. However, the synthetic polymer is not particularly limited as long as it has at least one hydroxyl group in the side chain substituent of the repeating unit.

The organic polymer of the present invention may be used alone or in combination of two or more kinds. The weight average molecular weight of the organic polymer is preferably 10 ³ to 10 ⁶ , and more preferably 5 × 10 ³ to 4 × 10 ⁵ .

In the composite of the (semi) metal-containing resin and the organic polymer, the ratio of the (semi) metal-containing resin and the organic polymer can be selected within a wide range, but the (semi) metal-containing resin / organic polymer mass ratio is preferable. 10/90 to 90/1
0, more preferably 20/80 to 80/20. Within this range, the strength of the image-receiving layer film and the water resistance to dampening water during printing will be good.

In the binder resin containing the complex of the present invention, the hydroxyl group of the (semi) metal-containing resin produced by the hydrolytic polycondensation of the compound and the specific bonding group in the organic polymer act as a hydrogen bond. As a result, a uniform organic-inorganic hybrid is formed, and it becomes microscopically homogeneous without phase separation. When a hydrocarbon group is present in the (semi) metal-containing resin, it is presumed that the affinity with the organic polymer is further improved due to the hydrocarbon group. Further, this composite has excellent film forming properties.

The composite of the present invention is produced by subjecting the compound to hydrolysis polycondensation and mixing with an organic polymer, or by subjecting the silane compound to hydrolysis polycondensation in the presence of an organic polymer. It

Preferably, an organic / inorganic polymer composite can be obtained by hydrolytic polycondensation of the above compound by a sol-gel method in the presence of an organic polymer. In the produced organic / inorganic polymer composite, the organic polymer is uniformly dispersed in the gel matrix (that is, the three-dimensional fine network structure of the inorganic metal oxide) produced by the hydrolytic polycondensation of the compound.

The sol-gel method as the above-mentioned preferable method can be carried out by using a conventionally known sol-gel method. Specifically, "Sol-gel method for thin film coating" (Technical Information Association) (published) (1995), Sakubana Seo "Sol-gel method science" (agne Jofusha Co., Ltd.) ) (1988), Shira Hirashima "Technology for functional thin film formation by latest sol-gel method", Comprehensive Technology Center (published) (19)
1992).

The coating liquid for the image receiving layer is preferably an aqueous solvent, and further a water-soluble solvent is used together for the purpose of uniform liquefaction by suppressing precipitation during preparation of the coating liquid. As the water-soluble solvent, alcohols (methanol, ethanol, propyl alcohol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc.), ethers (tetrahydrofuran , Ethylene glycol dimethyl ether, propylene glycol dimethyl ether, tetrahydropyran, etc.), ketones (acetone, methyl ethyl ketone, acetylacetone, etc.), esters (methyl acetate, ethylene glycol monomethyl monoacetate, etc.), amides (formamide, N-methylformamide, etc.) Pyrrolidone, N-methylpyrrolidone, etc.) and the like, and 1 type or 2 types It may be used in combination with the above.

Further, in order to accelerate the hydrolysis and polycondensation reaction of the (semi) metal compound represented by the general formula (I), it is preferable to use an acidic catalyst or a basic catalyst in combination.

As the catalyst, an acid or basic compound 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) is used. The concentration at that time is not particularly limited, but if the concentration is high, the hydrolysis and polycondensation rates tend to be high. However, if a basic catalyst with a high concentration is used, a precipitate may be generated in the sol solution,
The concentration of the basic catalyst is preferably 1N (converted to a concentration in an aqueous solution) or less.

The type of acidic catalyst or basic catalyst is not particularly limited, but when it is necessary to use a catalyst having a high concentration, a catalyst composed of an element that hardly remains in the catalyst crystal grains after sintering is used. Good. Specifically, as the acidic catalyst, hydrogen halide such as hydrochloric acid, nitric acid, sulfuric acid,
Sulfurous acid, hydrogen sulfide, perchloric acid, hydrogen peroxide, carbonic acid, carboxylic acids such as formic acid and acetic acid, substituted carboxylic acids obtained by substituting R of structural formula RCOOH with other elements or substituents, sulfonic acids such as benzenesulfonic acid, etc. Examples of the basic catalyst include ammoniacal bases such as aqueous ammonia and amines such as ethylamine and aniline.

The image-receiving layer of the present invention may contain other components in addition to the above components.

As other components, inorganic pigment particles other than the surface-roughened particles of the present invention may be contained. For example, silica,
Alumina, kaolin, clay, zinc oxide, titanium oxide,
Examples thereof include calcium carbonate, barium carbonate, calcium sulfate, barium sulfate and magnesium carbonate. These other inorganic pigments are used within a range not exceeding 40 parts by mass with respect to 100 parts by mass as the total amount of the surface irregularity particles of the present invention. It is preferably within 20 parts by mass.

In addition, a crosslinking agent may be added to the image receiving layer in order to further improve the film strength. Examples of the cross-linking agent include compounds usually used as cross-linking agents. Specifically, Shinzo Yamashita and Tosuke Kaneko, "Handbook for Crosslinking Agents," published by Taiseisha (1981), "Polymer Data Handbook, Basic Edition," edited by the Society of Polymer Science, Baifukan (198)
6 years) and the like can be used.

For example, ammonium chloride, metal ion,
Organic peroxides, polyisocyanate compounds (for example, toluylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, polymethylene phenyl isocyanate, hexamethylene diisocyanate, isophorone diisocyanate, high molecular polyisocyanate Nato, etc.), polyol compound (for example, 1,4-butanediol, polyoxypropylene glycol, polyoxyethylene glycol, 1,1,1
-Trimethylolpropane, etc.), polyamine compounds (for example, ethylenediamine, γ-hydroxypropylated ethylenediamine, phenylenediamine, hexamethylenediamine, N-aminoethylpiperazine, modified aliphatic polyamines, etc.), polyepoxy group-containing compounds and epoxies Resin (for example, "New Epoxy Resin" edited by Hiroshi Kakiuchi, Shokoido (1985), "Epoxy Resin" edited by Kuniyuki Hashimoto)
Compounds described in Nikkan Kogyo Shimbun (1969), etc.), melamine resin (for example, compounds described in "Uria Melamine Resin" edited by Ichiro Miwa and Hideo Matsunaga, Nikkan Kogyo Shimbun (1969)) , Poly (meth) acrylate compounds (for example, Shin Okawara, Takeo Saegusa, Toshinobu Higashimura, "Oligomer" Kodanmori (Published in 1976), Eizo Omori "Functional Acrylic Resin" Techno System (1985)
And the like).

The image-receiving layer of the present invention is formed by coating the above-mentioned coating liquid on a water-resistant support by any of the conventionally known coating methods and drying.

The thickness of the image receiving layer formed is 0.2 to 1
0 μm is preferable, and 0.5 to 8 μm is more preferable. Within this range, a film having a uniform thickness is formed, and the film has sufficient strength.

The image-receiving layer of the present invention preferably has a surface smoothness of 30 (sec / 10 mL) or more in terms of Beck's smoothness. Here, Beck's smoothness can be measured by a Beck's smoothness tester, and a test piece is placed on a highly smooth finished circular glass plate with a hole in the center at a constant pressure (1 kg / cm ² ). It measures the time required for a certain amount (10 mL) of air to be pressed and passed under reduced pressure between the glass surface and the test piece.

When plate making (image formation) is carried out by an electrophotographic printer, the preferable range of toner to be used is dry toner or liquid toner as follows.

In an electrophotographic printer using a dry toner, the Bekk smoothness of the image receiving layer surface of the original plate of the present invention is preferably 30 to 200 (sec / 10 mL), more preferably 50 to 150 (sec / 10 mL). Is. Within this range, in the process of transferring and fixing the toner image to the original plate, scattering toner is prevented from adhering to the non-image area (that is, scumming), and the toner adhesion in the image area is made uniform and sufficient. Good reproducibility of fine characters and uniformity of solid image area.

On the other hand, in an electrophotographic printer using a liquid toner, the Bekk smoothness of the surface of the image receiving layer is 30 (sec / 10 mL) or more, and the higher the better, the better 150-3000 (sec / sec).
10 mL), more preferably 200 to 2500 (seconds / 10 mL)
Is.

In the case of an ink jet type printer or a thermal transfer type printer, the same range as in the case of the electrophotographic printer using the liquid toner is preferable.

Within this range, high-definition toner image areas such as fine lines / fine characters and halftone images are faithfully transferred / formed on the image receiving layer, and the surface of the image receiving layer and the toner image area are sufficiently adhered. The image area strength can be maintained.

More preferably, the shape of the surface of the image receiving layer of the present invention is such that unevenness is high and the intervals are close.
Specifically, the surface center average roughness SRa defined by ISO-468 is in the range of 1.3 to 3.5 μm, and the average wavelength Sλa indicating the density of the surface roughness is in the range of 50 μm or less. preferable. More preferably, SRa is 1.
The range is 35 to 2.5 μm and Sλa is 45 μm or less. It is presumed that this suppresses the adhesion of the scattered toner to the non-image area after electrophotographic plate making and the thickening of the adhered toner during fixing.

Next, the water-resistant support used in the present invention will be described.

As the water resistant support, an aluminum plate,
Bimetal plate such as zinc plate, copper-aluminum plate, copper-stainless steel plate, chrome-copper plate, trimetal plate such as chrome-copper-aluminum plate, chrome-lead-iron plate, chrome-copper-stainless plate, etc. Is 0.1 to 3 mm, especially 0.
One of 1 to 1 mm is included. In addition, the thickness is 80 μm
Examples of the paper include a paper having a water resistance of 200 μm, a plastic film or a paper or a plastic film laminated with a metal foil.

The support used in the present invention preferably has a highly smooth surface. That is, the surface smoothness adjacent to the image receiving layer has a Beck's smoothness of 300 (sec / 10 m).
L) or more, more preferably 900 to 3000 (seconds / 10 m)
It is preferably adjusted to L), more preferably 1000 to 3000 (sec / 10 mL).

Image reproducibility and printing durability can be further improved by regulating the smoothness of the surface of the support on the side adjacent to the image receiving layer to be Beck smoothness of 300 (sec / 10 mL) or more. . Such an improving effect can be obtained even if the smoothness of the image receiving layer surface is the same,
It is considered that the increased smoothness of the surface of the support improved the adhesion between the image area and the image receiving layer.

The highly smooth surface of the water-resistant support regulated in this way refers to the surface on which the image-receiving layer is directly applied. For example, a conductive layer, an under layer, an over layer, which will be described later, may be formed on the support. When a coat layer is provided, its conductive layer,
It means the surface of the under layer and the overcoat layer.

As a result, the image-receiving layer having the surface-shaped bear adjusted as described above is sufficiently retained without being affected by the unevenness of the surface of the support, and the image quality can be further improved.

As a method for setting the above range of smoothness, various conventionally known methods can be used. Specifically, a method of melting and adhering the surface of the substrate with a resin, a method of adjusting the Bekk smoothness of the surface of the support by a method such as a calender strengthening method using a highly smooth heat roller, and the like can be mentioned.

The direct drawing type lithographic printing plate precursor of the present invention forms a toner image on an image receiving layer provided on a water resistant support by an electrophotographic recording method, or discharges an oil-based ink by utilizing an electrostatic field. It can also be preferably used as a lithographic printing plate precursor used for forming an image by the electrostatic discharge type inkjet method, and the lithographic printing plate obtained by image formation can print a large number of clear images. Is.

The image formation by the electrophotographic recording method is usually an electrophotographic process, and the transfer of the toner image onto the transfer material is performed by electrostatic transfer. The water-resistant support as the printing plate precursor is preferably electrically conductive, and particularly has a volume specific resistance value of 10 ⁴ to 10 ¹³ Ω · cm, and more preferably 10 ⁷ to 10 ¹² Ω · cm. As a result, bleeding / distortion of the transferred image, toner adhesion stains on the non-image area, and the like are suppressed to a level where there is no practical problem, and a good image is obtained.

Also in the image formation by the electrostatic discharge type ink jet recording system, it is preferable that the water resistant support is conductive, and at least the portion immediately below the image receiving layer is 10 ¹⁰ Ω · cm. It preferably has the following specific electric resistance value, and more preferably 10 ¹⁰ Ω · cm or less for the entire water resistant support. The above-mentioned specific electric resistance value is more preferably 10 ⁸ Ω · cm or less, and the value may be infinitely zero. When the conductivity is within the above range, when the charged ink droplets adhere to the image receiving layer, the charge of the ink droplets quickly disappears through the ground plane, so that a clear image without disturbance is formed. .

The measurement of the specific electric resistance value (also called the volume specific electric resistance value or the specific electric resistance value) is based on JIS.
It was carried out by a three-terminal method in which a guard electrode was provided according to K-6911.

In order to give the above-mentioned conductivity to the portion of the support directly below the image-receiving layer, a layer comprising a conductive filler such as carbon black and a binder is provided on a substrate such as paper or film. Examples of the method include coating, attaching a metal foil, and depositing a metal.

On the other hand, examples of the conductive material having the entire support include conductive paper impregnated with sodium chloride, a plastic film mixed with a conductive filler such as carbon black, and a metal plate such as aluminum. Can be mentioned.

For example, it can be obtained by using a conductive base paper in which a substrate is impregnated with sodium chloride or the like and providing a conductive layer having water resistance on both surfaces thereof. Examples of the base paper used as the substrate include wood pulp paper, synthetic pulp paper,
A mixed paper of wood pulp paper and synthetic pulp paper can be used as it is. The thickness of the base paper is 80 μm to 2
00 μm is preferable.

The conductive layer is formed by applying a layer containing a conductive filler and a binder to both sides of the conductive paper. The thickness of the conductive layer applied is 5 μm to 2 μm.
0 μm is preferable.

As the conductive filler, particulate carbon black, graphite such as silver, copper, nickel,
Metal powders such as brass, aluminum, steel and stainless steel, tin oxide powders, flaky aluminum or nickel, fibrous carbon and the like can be mentioned.

As the resin used as the binder, various resins are appropriately selected and used. Specifically, as the hydrophobic resin, for example, acrylic resin, vinyl chloride resin, styrene resin, styrene-butadiene resin,
Examples of the hydrophilic resin include styrene-acrylic resin, urethane resin, vinylidene chloride resin, vinyl acetate resin, and the like. Examples of the hydrophilic resin include polyvinyl alcohol resin, cellulose derivative, starch and its derivative, polyacrylamide resin, and styrene. Examples thereof include maleic anhydride-based copolymers.

Another method for forming a conductive layer is to laminate a conductive thin film. As the conductive thin film, for example, a metal foil, a conductive plastic film or the like can be used. More specifically, examples of the metal foil laminate include aluminum foil, and examples of the laminate of the conductive plastic film include polyethylene resin mixed with carbon black. The aluminum foil may be either hard or soft, and the thickness is 5μ.
m to 20 μm is preferable.

An extrusion laminating method is preferable for laminating a polyethylene resin mixed with carbon black. The extrusion laminating method is a method in which a polyolefin is heat-melted and formed into a film, which is immediately pressed onto a base paper,
It is a method of cooling and laminating, and various devices are known. The thickness of the laminate layer is 10 μm to 30 μm
Is preferred. Assuming that the entire support has conductivity,
When a plastic film or metal plate having conductivity is used as the substrate, it can be used as it is if the water resistance is satisfied.

As the plastic film having conductivity, for example, polypropylene or polyester film mixed with conductive filler such as carbon fiber or carbon black can be used, and as the metal plate, aluminum or the like can be used. The thickness of the substrate is preferably 80 μm to 200 μm. If it is less than 80 μm, the strength of the printing plate is insufficient,
When it exceeds 200 μm, the handling property such as the transportability in the drawing device is deteriorated.

Next, the structure in which the conductive layer is provided will be described.

The water resistant substrate has a thickness of 80 μm to 20 μm.
Paper having a water resistance of 0 μm, plastic film, paper laminated with metal foil, plastic film, or the like can be used.

As the method for forming the conductive layer on the substrate, the method described in the case where the whole support has conductivity can be used. That is, a layer containing a conductive filler and a binder is applied to one surface of the substrate in a thickness of 5 μm to 20 μm. Alternatively, it can be obtained by laminating a metal foil or a conductive plastic film.

As a method other than the above, for example, a metal vapor deposition film of aluminum, tin, palladium, gold or the like may be provided on a plastic film.

As described above, a water resistant support having conductivity can be obtained.

In the present invention, as described above, a back coat layer (back surface layer) can be provided on the surface of the support opposite to the image receiving layer for the purpose of preventing curling. However, the back coat layer has a smoothness. It is preferably in the range of 150 to 700 (second / 10 mL). As a result, when the printing plate is supplied to the offset printing machine, the printing plate is accurately set in the printing machine without causing misalignment or slippage.

The thickness of the water resistant support provided with the under layer or the back coat layer is in the range of 90 to 130 μm, preferably 100 to 120 μm.

An image is formed on the lithographic printing plate precursor of the present invention by a thermal transfer recording system, an electrophotographic recording system, an ink jet recording system or the like for plate making.

As the electrophotographic recording method, any conventionally known recording method can be used. For example, "Basics and Applications of Electrophotographic Technology" edited by The Electrophotographic Society of Japan, published by Corona Publishing Co., Ltd. (1988), Kenichi Eda, Journal of the Electrophotographic Society 27 ,
113 (1988), Akio Kawamoto, 33 , 149 (19)
94), Akio Kawamoto, 32 , 196 (1993), etc., or a commercially available PPC copying machine.

The combination of the scanning exposure method using laser light for exposing on the basis of digital information and the developing method using a liquid developer is an effective process because a high-definition image can be formed. An example is shown below.

First, the photosensitive material is positioned on the flat bed by the register pin method, and then suctioned and fixed by air suction from the back surface. Next, for example, the photosensitive material is charged by the charging device described in "Basics and Applications of Electrophotographic Technology", page 212 et seq. The corotron or scotron system is common. At this time, it is also preferable to control the charging condition by giving feedback so that the surface potential is always within a predetermined range based on the information from the charging potential detection means of the photosensitive material. Then, for example, scanning exposure with a laser light source is performed using the method described on page 254 and the like of the above cited material.

Next, a toner image is formed using the liquid developer. The light-sensitive material charged and exposed on a flat bed can be removed from it, and the wet development method shown on page 275 and after of the above-mentioned reference can be used. The exposure mode at this time corresponds to the toner image development mode. For example, in the case of reversal development, a negative image, that is, an image portion is irradiated with laser light to charge the photosensitive material with the same charge polarity. The toner having the toner is used and a developing bias voltage is applied so that the toner is electrodeposited on the exposed portion. The details of the principle are described on page 157 and after of the above cited material.

After the development, in order to remove the excessive developing solution, squeeze such as rubber roller, gap roller, reverse roller, etc. as shown on page 283 of the same material, squeeze such as corona squeeze, air squeeze, etc. are carried out. It is also preferable to rinse only with the carrier liquid of the developer before squeezing.

Next, the toner image formed as described above on the photoconductor is transferred onto the lithographic printing plate precursor that is the material to be transferred.
It is fixed, or is transferred and fixed on the lithographic printing plate precursor via an intermediate transfer member.

The ink jet recording method may be any of the conventionally known recording methods.
An oil-based ink is preferred because of its fixability, difficulty in clogging of ink, and the like, and an electrostatic discharge type inkjet method is preferred because it does not easily cause image bleeding. A solid jet method using hot melt ink is also preferably used.

On-demand ink jet system using electrostatic force Susumu Ichinose, Yuji Ohba, IEICE Transactions Vol.J66-C (No.1), p47 (1983), Tadayoshi Ohno, Mamoru Mizuguchi, IEICE A method called an electrostatic acceleration type ink jet or a slit jet described in magazines vol.10, (No.3), p157 (1981) and the like is known, and a specific embodiment thereof is, for example, JP-A-56-170, No. 56-4467, No. 57-
No. 151374 and the like.

This is because ink is supplied from the ink tank to the slit-shaped ink chamber in which a large number of electrodes are arranged on the inner surface of the slit-shaped ink holding portion, and a high voltage is selectively applied to these electrodes. The ink near the electrodes is ejected onto the recording paper that is in close proximity to the slit for recording.

As another method which does not use a slit-shaped recording head, Japanese Patent Laid-Open No. 61-211048 discloses that a hole is formed in a film-shaped ink support having a plurality of fine holes, and ink is filled in to form a multi-needle. A means for selectively applying a voltage by electrodes to move the ink in the holes to the recording paper is disclosed.

As the solid jet method, So
lid Inkjet Platemaker SJ02A (manufactured by Hitachi Koki Co., Ltd.),
A commercially available printing system such as MP-1200Pro (manufactured by Dynic Corporation) can be used.

The plate making method using the ink jet recording method will be described more specifically with reference to the drawings.

The apparatus system shown in FIG. 1 has an ink jet recording apparatus 1 which uses oil-based ink.

As shown in FIG. 1, first, pattern information of an image (graphic or text) to be formed on the master (lithographic printing original plate) 2 is transmitted from an information supply source such as the computer 3 via the bus 4. Then, the ink is supplied to the inkjet recording apparatus 1 using the oil-based ink. The ink jet recording head 10 of the recording apparatus 1 stores oil-based ink therein, and when the master 2 passes through the recording apparatus 1, minute droplets of ink are sprayed onto the master 2 according to the above information. As a result, the ink adheres to the master 2 in the above pattern.

In this way, an image is formed on the master 2 to obtain a plate-making master (a plate-making printing original plate).

An example of an ink jet recording apparatus used in the apparatus system of FIG. 1 is shown in FIGS. 2 and 3. 2 and 3
In FIG. 1, members common to those in FIG. 1 are designated by common reference numerals.

FIG. 2 is a schematic configuration diagram showing a main part of such an ink jet recording apparatus, and FIG. 3 is a partial sectional view of a head.

The head 10 provided in the ink jet recording apparatus is, as shown in FIG.
01 and the lower unit 102 have a slit sandwiched between them, the tip of which is an ejection slit 10a, the ejection electrode 10b is disposed in the slit, and the oil ink 11 is filled in the slit. Has become.

In the head 10, a voltage is applied to the ejection electrode 10b according to the digital signal of the image pattern information. As shown in FIG. 2, the counter electrode 10c is installed so as to face the ejection electrode 10b.
The master 2 is provided above. By applying a voltage, a circuit is formed between the ejection electrode 10b and the counter electrode 10c, the oil-based ink 11 is ejected from the ejection slit 10a of the head 10, and an image is formed on the master 2 provided on the counter electrode 10c. It is formed.

The width of the discharge electrode 10b is preferably as narrow as possible in order to form a high quality image.

For example, the head 10 shown in FIG. 3 is filled with the oil-based ink, the tip of the ejection electrode 10b is 20 μm wide, and the distance between the ejection electrode 10b and the counter electrode 10c is 1.5 mm.
By applying a voltage of 3 kV for 0.1 msec between the electrodes, it is possible to form dots of 40 μm on the master 2.

As described above, on the lithographic printing plate precursor,
A printing plate can be prepared by forming an image by an inkjet method using an oil-based ink.

[0168]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Example 1 Needle-like particles (conductive titanium oxide FT2000, manufactured by Ishihara Sangyo Co., Ltd. average diameter 0.1 μm, average length 2 μm) 10
0 g, 113 g of a 10 wt% aqueous solution of polyvinyl alcohol (PVA203, manufactured by Kuraray Co., Ltd.) and 300 g of a 0.1 N silver nitrate aqueous solution were mixed and preliminarily hydrolyzed to a liquid dispersed for 30 minutes with a paint shaker (Toyo Seiki Co., Ltd.). 107 g of a 20 wt% tetramethoxysilane water / ethanol (1: 1) solution prepared above was mixed with 182 g of 20% aqueous colloidal silica solution Snow Tech C (Nissan Chemical Co., Ltd.). Support for ELP-1X type master (manufactured by Fuji Photo Film Co., Ltd.) used as an electrophotographic planographic printing original plate for light printing (Beck smoothness on the under side: 1
000 (sec / 10 mL)) was coated with a wire bar so that the coating amount after drying was 5 g / m ² and dried in an oven at 100 ° C. for 10 minutes. Then, by irradiating with a 100 W high pressure mercury lamp through a Pyrex (registered trademark) filter for 2 minutes,
Black metallic silver was deposited on the surface of the acicular particles (precipitation method 1).

The reflection optical density of the printing original plate thus produced was 1.12 (measurement was carried out according to the international standard ISO5).
-3 and 5-4 with a densitometer (X-
RITE densitometer) using neutral color all visible light range filter).

The lithographic printing plate precursor was measured for its smoothness using a Beck's smoothness tester (manufactured by Kumagai Riko Co., Ltd.) under an air volume of 10 mL, and found to be 105 (sec / 10 mL). Further, 2 μl of distilled water was placed on the surface of the lithographic printing plate precursor, and the surface contact angle (degree) after 30 seconds was measured using a surface contact angle meter (trade name CA-D, manufactured by Kyowa Interface Science Co., Ltd.). It was 5 degrees or less.

The lithographic printing plate precursor described above was converted to "AM-Straig
"HT Imaging System" commercially available laser printer using dry toner AMSIS 1200-
The plate was made through J Plate Setter (trade name).

The copy image of the obtained plate-making product was visually evaluated with a magnifying glass of 20 times, and the plate-making image quality was good. That is, the plate-making product of the present invention obtained by dry-type toner transfer from a laser printer has no thin lines or fine characters, the solid part is uniform, and no unevenness in toner transfer is observed at all. Also, the background fog caused by the toner scattering was slight and it was a good one with no practical problems.

Next, after making the above lithographic printing plate precursor by the same operation as described above, a fully automatic printing machine AM-2850 (trade name, manufactured by AM Co., Ltd.) was used to prepare P as fountain solution.
A solution obtained by diluting S-plate processing agent EU-3 (manufactured by Fuji Photo Film Co., Ltd.) 50 times with distilled water was placed in a fountain solution tray, and printing was performed using an ink ink for offset printing. . The printed image (ground fog, solid uniformity in the image area) of the 10th printed matter was visually evaluated using a 20-fold magnifying glass, and it was extremely good.

Further, 30,000 or more good prints were obtained which had an image without fine lines, missing fine characters and uneven solid areas and had no practical problems with ink stains on non-image areas.

The original plate of the present invention can produce a large number of good printed matters. Comparative Example 1 A lithographic printing plate precursor was prepared in the same manner as in Example 1 except that the 0.1 N silver nitrate aqueous solution of the image receiving layer composition was changed to distilled water.

The Beck smoothness of the surface of the obtained original plate is 16
The contact angle with water was 0 degree (sec / 10 mL) and 5 degrees or less.

The above original plate was prepared and printed in the same manner as in Example 1. The image quality of the plate made was almost the same as that of Example 1, and the amount of scattered toner in the non-image area was small and the image was good. However, the printed matter was good in printing without any stain on the non-image area, but the image area was missing after printing about 1000 sheets. Example 2 <Preparation of lithographic printing plate precursor for direct drawing> The following composition was used together with glass beads in a paint shaker (Toyo Seiki Co., Ltd.).
After being dispersed at room temperature for 20 minutes, the glass beads were filtered to obtain a dispersion.

Needle-shaped particles (conductive titanium oxide FT2000, manufactured by Ishihara Sangyo Co., Ltd., average diameter 0.1 μm, average length 2 μm) 100 g, 10 wt% aqueous solution of gelatin (Wako Pure Chemical Industries, Ltd.) 300 g tetraethoxysilane 25 g Ethanol 8.6 g Colloidal silica 20% aqueous solution; Snow Tech C (Nissan Chemical Industry Co., Ltd.) 18 g Fluorinated alkyl ester; FC-430 (manufactured by 3M) 0.25 g Curing agent CH ₂ = CHSO ₂ CH ₂ CONH ( CH ₂ ) ₃ NHCOCH ₂ SO ₂ CH = CH ₂ 1.0 g 1 N hydrochloric acid 4 g 0.1 N silver nitrate aqueous solution 250 g ELP-2X type master (Fuji Photo Film ( Co., Ltd.)
Support (Under one side Beck smoothness: 2000 (se
c / 10 mL) or more), and the above composition is applied thereto by using a wire bar so that the coating amount after drying is 6 g / m ² , dried by touch with a finger, and further heated at 110 ° C. for 30 minutes. After that, in the same manner as in the precipitation method 1 of Example 1, metallic silver was deposited on the surfaces of the acicular particles to prepare a lithographic printing plate precursor.

The Beck's smoothness of the surface of the obtained original plate is 70.
0 (sec / 10 mL), the contact angle with water was 5 degrees or less. <Preparation of electrophotographic photoreceptor> 2 g of X-type metal-free phthalocyanine (manufactured by Dainippon Ink and Chemicals, Inc.), the following binder resin (P-
1) 14.4 g, the following binder resin (P-2) 3.6 g, the following compound (A) 0.15 g and cyclohexanone 80 g
Put the mixture of the above together with glass beads in a 500 mL glass container and use a paint shaker (Toyo Seiki Seisakusho)
After dispersion for 0 minutes, the glass beads were filtered to obtain a photosensitive layer dispersion liquid.

[0180]

[Chemical 4]

Next, the dispersion was degreased to a density of 0.
Apply on a 2mm thick aluminum plate with a wire bar,
After being dried by touch, it was heated in a circulating oven at 110 ° C. for 20 seconds. The film thickness of the obtained photosensitive layer was 8 μm.

The electrophotographic photosensitive member prepared as described above was corona-charged in the dark to have a surface potential of +450 V, which was then read from a document by a color scanner in advance and color-separated to obtain a system-specific number. After making corrections related to color reproduction, using a semiconductor laser drawing device as an exposure device, a beam of 788 mm was obtained based on the information stored in the hard disk in the system as digital image data. Exposure was performed with a spot diameter of 15 μm and a pitch of 10 μm and a scan speed of 300 cm / sec (that is, 2500 dpi). Exposure was performed so that the exposure amount on the photoconductor at this time was 25 erg / cm ² .

Subsequently, the liquid developer having the following contents is used for development, followed by rinsing in a bath of Isopar G to remove stains on the non-image area. Then, the surface temperature of the photoconductor is adjusted to 50 ° C. with warm air. It was dried so that the remaining amount of Isopar G was 10 mg / g toner weight. Subsequently, this photoreceptor was precharged with a corona charger at -6 KV, the image surface of this photoreceptor was superposed on the above-mentioned lithographic printing plate precursor, and negative corona discharge was applied from the electrophotographic photoreceptor side to transfer. <Liquid developer> Mix the components of the following composition in a kneader and
The mixture was kneaded at 5 ° C. for 2 hours to obtain a mixture. The mixture was cooled in a kneader and then ground in the same kneader. 1 part by weight of this pulverized product and 4 parts by weight of Isopar H were dispersed for 6 hours with a paint shaker to obtain a dispersion. This dispersion was diluted with Isopar G so that the toner solid content was 1 g per liter, and at the same time, 0.1 g per liter of basic barium petrone was added as a charge control agent for imparting a negative charge property. A developer was prepared. (Composition for kneading) 4 parts by weight of ethylene / methacrylic acid copolymer (Mitsui DuPont, Nucrel N-699) Carbon black # 30 (manufactured by Mitsubishi Kasei) 1 part by weight Isopar L (manufactured by Exxon) 15 parts by weight Of the lithographic printing plate (plate making) on which a partial image is formed at a temperature of 100
The toner image area was completely fixed by heating at 30 ° C. for 30 seconds.

The drawn image of the obtained plate-making product was evaluated by observing with an optical microscope at a magnification of 200 times. It was a clear image with no blurring or loss of fine lines or characters.

Next, the printing plate prepared as described above is
As a printing machine, Oliver 94 type (made by Sakurai Manufacturing Co., Ltd.)
SLM-OD (Mitsubishi Paper Mills, Ltd.)
A solution prepared by diluting 100% by volume with distilled water was placed in a dampening water tray portion, and printing was performed using black ink for offset printing.

When the printed image of the 10th printed matter was visually evaluated using a 20 times magnifying glass, no background stain was found due to the adhered printing ink in the non-image area, and the uniformity of the solid image area was good. there were. Further, even when observed with an optical microscope at a magnification of 200 times, fine lines, thinning of fine characters, missing, etc. were not recognized, and the image quality was good.

[0187] 30,000 or more printed matter having a print quality equivalent to this was obtained. Example 3 <Preparation of Water-Resistant Support> A high-quality paper weighing 100 g / m ² was used as a substrate, a back layer coating composition having the following composition was applied to one surface of the substrate using a wire bar, and a dry coating amount was applied. 12 g /
After providing the back layer of m ^2, the back layer has a smoothness of 100.
Calendar treatment was performed so that the time would be about (sec / 10 mL). (Paint for back coat layer) -Kaolin (50% aqueous dispersion) 200 parts-Polyvinyl alcohol aqueous solution (10%) 60 parts-SBR latex (solid content 50%, Tg: 0 ° C) 100 parts-Melamine resin (solid content) 80%, Sumirez resin SR-613) 5 parts Next, a coating for an under layer having the following composition is applied to the other surface of the substrate using a wire bar, and a dry coating amount is 10 g / m ²
After providing the under layer, the under layer has a smoothness of 150.
Calendar processing was performed so that it was about 0 (sec / 10 mL). (Paint for under layer) -Carbon black (30% aqueous dispersion) 5.4 parts-Clay (50% aqueous dispersion) 54.6 parts-SBR latex (solid content 50%, Tg: 25 ° C) 36 parts- Melamine resin (solid content 80%, Sumirez resin SR-613) 4 parts The above components were mixed, and water was added so that the total solid content was 25% to obtain an under layer coating material.

The specific electric resistance value of the obtained under layer is
It measured as follows.

The under layer coating material was applied onto a stainless steel plate that had been thoroughly degreased and washed to obtain a coating film having a dry coating amount of 10 g / m ² . With respect to the obtained sample, the specific electric resistance value thereof was set to 3 according to JIS K-6911 and provided with a guard electrode.
It was measured by the terminal method and a value of 4 × 10 ⁹ Ω · cm was obtained. <Preparation of lithographic printing plate precursor for direct drawing> The following composition was dispersed together with glass beads in a paint shaker (Toyo Seiki Co., Ltd.) at room temperature for 20 minutes, and the glass beads were filtered to obtain a dispersion.

Needle-shaped particles (conductive titanium oxide FT2000, manufactured by Ishihara Sangyo Co., Ltd., average diameter 0.1 μm, average length 2 μm) 100 g Starch (PENON ZP-2, manufactured by Nippon Starch Chemical Co., Ltd.) 10% aqueous solution 300 g Tetraethoxysilane 30g Methyltrimethoxysilane 3g Snowtech C (20% aqueous solution) 91g Ethanol 10g 1N Hydrochloric acid 5g 0.1N Copper sulfate aqueous solution 300g This dispersion was placed on the above water resistant support using a wire bar. The coating method was applied so that the coating amount after drying was 6 g / m ^2, and was dried in an oven at 100 ° C. for 20 minutes, and then the precipitation method 1 of Example 1 was used.
In the same manner as above, metallic copper was deposited on the surface of the acicular particles to prepare a printing original plate. <Preparation of oil-based ink (IK-1)> (Production of resin particles) Poly (dodecyl methacrylate) 1
A mixed solution of 4 g, 100 g of vinyl acetate, 4.0 g of octadecyl methacrylate and 286 g of Isopar H was heated to 70 ° C. while stirring under a nitrogen stream. As a polymerization initiator, 1.5 g of 2,2'-azobis (isovaleronitrile) (abbreviation AIVN) was added and reacted for 4 hours. Furthermore, 0.8 g of 2,2'-azobis (isobutyronitrile) (abbreviation AIBN) was added, and then the mixture was heated to a temperature of 80 ° C. and reacted for 2 hours, and then A ．
I. B. N. 0.6 g was added and reacted for 2 hours. Then, the temperature was raised to 100 ° C. and the mixture was stirred as it was for 1 hour to distill off unreacted monomers. After cooling, the white dispersion obtained through a 200-mesh nylon cloth was a latex having a polymerization rate of 93% and an average particle size of 0.35 μm. Particle size is CAP
It was measured with A-500 (manufactured by Horiba, Ltd.). (Preparation of Ink) 10 g of dodecyl methacrylate / acrylic acid copolymer (copolymerization ratio: 98/2 weight ratio), 10 g of alkali blue and 71, 30 g of Shellzol together with glass beads, Paint shaker (Toyo Seiki Co., Ltd.)
Product) and dispersed for 4 hours to obtain a fine blue dispersion of alkali blue.

50 g (as solid content) of the above resin particles, 5 g (as solid content) of the above blue dispersion, and 0.06 g of zirconium naphthenate were diluted to 1 liter of Isopar G to obtain a blue oil-based ink (IK-1). )
It was created.

[0192] The original plate obtained above can be used to draw a personal computer output.
8400 is modified, the ink discharge head shown in FIG. 2 is attached to the pen plotter, and the above oil-based ink (IK-1) is applied to the lithographic printing plate precursor that is installed on the counter electrode with a gap of 1.5 mm. Was used to make a plate. At the time of plate making, the under layer provided directly below the image receiving layer of the printing original plate and the counter electrode were electrically connected using a silver paste.

The plate-made plate was adjusted with a Ricoh Fuser (manufactured by Ricoh Co., Ltd.) to a plate surface temperature of 70 ° C.
The ink image was fixed by heating for 2 seconds.

The drawn image of the obtained plate-making product was evaluated by observing it with an optical microscope at a magnification of 200 times. It was a clear image with no blurring or loss of fine lines or characters.

Next, the printing plate prepared as described above is
As a printing machine, Oliver 94 type (made by Sakurai Manufacturing Co., Ltd.)
As a dampening water, a solution prepared by diluting EU-3 (manufactured by Fuji Photo Film Co., Ltd.) 100 times with distilled water was put in a dampening water tray part and printing was performed using black ink for offset printing. I did.

When the printed image of the 10th printed matter was visually evaluated using a magnifying glass of 20 times, no background stain was found due to the adhered printing ink in the non-image area, and the uniformity of the solid image area was good. Met. Even with a 200x optical microscope observation,
No fine lines or thin characters, no missing, etc. were observed, and the image quality was good.

30,000 or more printed matter having a print quality equivalent to this was obtained. Examples 4 to 10 In Example 1, the PVA203 of the coating liquid for the image receiving layer was used.
And, instead of tetramethoxysilane, 24 g of the organic polymer and 24 g of the silane compound shown in Table 1 below were used,
A lithographic printing plate precursor was prepared in the same manner as in Example 1.

[0198]

[Table 1]

The Beck smoothness of the surface of each obtained original plate is 1
Within the range of 20 to 150 (sec / 10 mL), the contact angle with water was 5 degrees or less.

A printing plate was prepared by making a plate in the same manner as in Example 1, and when printing was performed, all of the obtained prints had a clear image quality with no stain in the non-image areas, as in the prints of Example 1. The printing durability was as good as 30,000 sheets or more. Example 11 The following composition was dispersed with a paint shaker for 20 minutes to form a dispersion, which was then coated on a support for ELP-2X using a wire bar so that the coating amount after drying was 6 g / m ^2. Then
It was dry to the touch. Then, after heating at 150 ° C. for 30 minutes, metal silver was deposited on the surface of the acicular particles in the same manner as in the precipitation method 1 of Example 1 to prepare a lithographic printing plate precursor. <Image receiving layer composition> Needle-like particles (conductive titanium oxide FT2000, manufactured by Ishihara Sangyo Co., Ltd. average diameter 0.1 μm, average length 2 μm) 45 g Silica: Silysia 310 (manufactured by Fuji Silysia Chemical Ltd.) 5 g Amber Acid-modified starch PENON-F3 (manufactured by Nitto Kagaku Co., Ltd.) 30 g Tetraethoxysilane 28 g Benzyltrimethoxysilane 2 g 1 N hydrochloric acid 2 g 0.1 N silver nitrate aqueous solution 300 g The obtained image-receiving layer has a Beck smoothness of 300 (Se
c / 10 mL), and the contact angle with water was 5 degrees or less.

Plate making was carried out using the recording apparatus of Example 3 and the oil-based ink. The image quality of the obtained plate-making product was clear with no distortion or bleeding in a fine image such as fine lines and fine characters.

Next, when printing was carried out in the same manner as in Example 3, the printed matter obtained had clear image quality with no stains on the non-image areas, and printing durability, as in the case of the printed matter of Example 3. It was a good one with 30,000 sheets or more. Examples 12 to 25 Lithographic printing plate precursors were prepared in the same manner as in Example 3 except that the acicular particles of the image receiving layer component were changed to the metal compound particles shown in Table 2 below. The Bekk smoothness of the surface of each original plate is 400 to 8
It was 00 (sec / 10 mL). When the contact angle on the surface of the original plate was measured, it was 5 degrees or less.

For each original plate, a plate was made and printed in the same manner as in Example 3. The obtained printed matter was a clear image with no background stains on the non-image area and no blurring or distortion of fine lines and characters, and as shown in Table 2, each plate had a good quality of 30,000 or more. Showed excellent printing durability.

[0204]

[Table 2]

Examples 26 to 42 A lithographic printing plate precursor was prepared in the same manner as in Example 11 except that the aqueous solution of silver nitrate of the image receiving layer component was changed to the aqueous solution of metal salt shown in Table 3 below. The Bekk smoothness of the surface of each original plate is 300.
It was ~ 850 (sec / 10 mL). When the contact angle on the surface of the original plate was measured, it was 5 degrees or less.

Each original plate was prepared and printed in the same manner as in Example 3. The obtained printed matter has a clear image with no background stains on the non-image area and no blurring or distortion of fine lines and characters, and as shown in Table 3, each plate has a good quality of 30,000 or more. Showed excellent printing durability.

[0207]

[Table 3]

Example 43 Needle-like particles (conductive titanium oxide FT2000, manufactured by Ishihara Sangyo Co., Ltd. average diameter 0.1 μm, average length 2 μm) 20
0 g was mixed with 600 g of a 0.1 N silver nitrate aqueous solution, and the mixture was irradiated with a 100 w high pressure mercury lamp through a Pyrex filter for 3 minutes while stirring. Then filter the particles,
It was washed with 1 liter of water and dried to obtain titanium oxide particles in which black metallic silver was deposited on the surface of the particles.

100 g of the above needle-shaped particles, 113 g of a 10 wt% aqueous solution of polyvinyl alcohol (PVA203, manufactured by Kuraray Co., Ltd.) and 300 g of water were mixed, and dispersed in a paint shaker (manufactured by Toyo Seiki Co., Ltd.) for 30 minutes, Pre-hydrolyzed 20 wt% tetramethoxysilane water /
107g ethanol (1: 1) solution and 20% colloidal silica aqueous solution Snowtex C (Nissan Chemical Co., Ltd.)
182 g), and the above image-receiving layer composition was applied to a support of an ELP-1X type master by using a wire bar so that the coating amount after drying was 5 g / m ² , and the mixture was dried in an oven. It was dried at 100 ° C. for 10 minutes.

The lithographic printing plate precursor thus prepared had a Bekk smoothness of 110 (sec / 10 mL) and a contact angle with water of 5
It was below the degree.

The above lithographic printing plate precursor was subjected to plate making and printing in the same manner as in Example 1, and as a result, the printed image (background fog, solid uniformity of image area) of the tenth printed sheet was
It was extremely good. Furthermore, 30,000 or more good prints were obtained which had an image without fine lines, missing fine characters and uneven solid areas and had no practical problems with ink stains on non-image areas. Example 44 Needle-like particles (potassium titanate whiskers Tismo N,
Otsuka Chemical Co., Ltd., average diameter 0.4 μm, average length 15
(100 μm) was mixed with 600 g of a 0.1 N silver nitrate aqueous solution, and the mixture was irradiated with a 100 w high-pressure mercury lamp through a Pyrex filter for 2 minutes while stirring. Then, the particles were filtered, washed with 1 liter of water and dried to obtain needle-shaped particles in which black metallic silver was deposited on the surface of the particles.

A lithographic printing plate precursor was prepared in the same manner as in Example 43 except that the above acicular particles were used.

The lithographic printing plate precursor thus prepared had a Bekk smoothness of 125 (sec / 10 mL) and a contact angle with water of 5
It was below the degree.

This lithographic printing plate precursor is a solid jet recording type Solid Injet Platemaker SJO2A (Hitachi Koki Co., Ltd.).
Plate was produced by using the same method as in Example 1, and as a result, the print image of the 10th printed sheet (background fog,
The solid uniformity in the image area) was extremely good. Furthermore, 30,000 or more good prints were obtained which had an image without fine lines, missing fine characters and uneven solid areas and had no practical problems with ink stains on non-image areas. Examples 45 to 56 Preparation of surface uneven particles <Preparation of surface uneven particles 1> Needle-like particles (conductive titanium oxide FT1000, manufactured by Ishihara Sangyo Co., Ltd., average diameter 0.1 μm)
m, average length 1.5 μm) 100 g, methanol 200
20 g of 3-aminopropyltrimethoxysilane (manufactured by Chisso Corporation) was added, and the mixture was stirred for 1 hour and the surface was subjected to a coupling treatment. Then, the supernatant was removed. Next, 100 g of colloidal silica (Snowtex C, manufactured by Nissan Kagaku Co., Ltd.) having an average particle diameter of 0.02 μm was added, and the mixture was stirred for 2 hours, left to stand for 10 minutes, the supernatant was removed, and vacuum dried,
Needle-like particles having silica particles having an average particle diameter of 0.02 μm adsorbed on the surface were obtained. <Preparation of surface uneven particles 2> Needle-like particles (conductive titanium oxide FT1000, manufactured by Ishihara Sangyo Co., Ltd., average diameter 0.1 μm)
m, average length 1.5 μm) 100 g, methanol 200
20 g of 3-aminopropyltrimethoxysilane (manufactured by Chisso Corporation) was added, and the mixture was stirred for 1 hour and the surface was subjected to a coupling treatment. Then, the supernatant was removed. Next, an alumina sol having an average particle diameter of 0.02 μm (alumina sol 52
0, manufactured by Nissan Kagaku Co., Ltd.) was added, and the mixture was stirred for 2 hours, allowed to stand for 10 minutes, the supernatant was removed, and vacuum dried.
Needle-like particles having alumina particles having an average particle diameter of 0.02 μm adsorbed on the surface were obtained. <Creation of surface uneven particles 3> Needle-like particles (conductive titanium oxide FT1000, manufactured by Ishihara Sangyo Co., Ltd., average diameter 0.1 μm)
m, average length 1.5 μm) 100 g, methanol 200
20 g of 3-aminopropyltrimethoxysilane (manufactured by Chisso Corporation) was added, and the mixture was stirred for 1 hour and the surface was subjected to a coupling treatment. Then, the supernatant was removed. Next, 100 g of colloidal silica particles having an average particle diameter of 0.02 μm (Snowtex C, manufactured by Nissan Kagaku Co., Ltd.) was added, and the mixture was stirred for 2 hours, allowed to stand for 10 minutes, the supernatant was removed, and vacuum dried to obtain a surface. Needle-like particles having silica particles having an average particle diameter of 0.02 μm adsorbed on the glass were obtained. <Preparation of surface uneven particles 4> Needle-like particles (conductive titanium oxide FT1000, manufactured by Ishihara Sangyo Co., Ltd., average diameter 0.1 μm)
m, average length 1.5 μm) 100 g, distilled water 200 g
To the above, 100 g of colloidal silica (Snowtex C, manufactured by Nissan Kagaku Co., Ltd.) having an average particle size of 0.02 μm was added, and the mixture was stirred for 2 hours, left to stand for 10 minutes, the supernatant was removed, vacuum dried, and the surface was averaged. Needle-like particles with surface irregularities having an average particle size of 0.4 μm were obtained which were adsorbed by silica particles having a particle size of 0.02 μm. <Creation of surface irregularity particles 5> Needle-like particles (conductive titanium oxide FT1000, manufactured by Ishihara Sangyo Co., Ltd., average diameter 0.1 μm)
m, average length 1.5 μm) 100 g, distilled water 200 g
Then, 100 g of an alumina sol (alumina sol 520, manufactured by Nissan Kagaku Co., Ltd.) having an average particle size of 0.02 μm was added, and the mixture was stirred for 2 hours, allowed to stand for 10 minutes, the supernatant was removed, and vacuum dried to obtain an average particle size on the surface. Needle-shaped particles with surface irregularities having an average particle size of 0.4 μm, in which 0.02 μm of alumina particles were adsorbed, were obtained. <Creation of surface irregularity particles 6> Needle-like particles (conductive titanium oxide FT1000, manufactured by Ishihara Sangyo Co., Ltd. average diameter 0.1 μm)
m, average length 1.5 μm) 100 g, and average particle size 0.
100 μg of 02 μm colloidal silica (Snowtex C, manufactured by Nissan Kagaku Co., Ltd.) was added, and the mixture was stirred for 2 hours, and silica particles with an average particle size of 0.02 μm were adsorbed on the surface. The particles were obtained. <Creation of surface irregularity particles 7> Needle-like particles (conductive titanium oxide FT1000, manufactured by Ishihara Sangyo Co., Ltd., average diameter 0.1 μm)
m, average length 1.5 μm) 100 g to 500 g of 1N NaO
It was immersed in H and sonicated for 30 minutes to make the surface hydrophilic. Then, the supernatant liquid is removed and washed with water, and methanol 200
20 g of (3-glycidoxypropyl) trimethoxysilane (manufactured by Chisso Corporation) was added, and the mixture was stirred for 1 hour, and the surface was subjected to a coupling treatment. Then, the supernatant was removed. Next, titania particles (STS0
1, Ishihara Sangyo Co., Ltd.) 100 g, methanol 200
20 g of 3-aminopropyltrimethoxysilane (manufactured by Chisso Corporation) was added, and the mixture was stirred for 1 hour, and the surface was subjected to a coupling treatment. Then, 100 g of the above-mentioned surface-treated silica particles was added, and the mixture was stirred for 2 hours, allowed to stand for 10 minutes, the supernatant was removed, and vacuum dried to obtain an average particle diameter of 0.01 μ
Needle-like particles with surface irregularities having an average particle diameter of 2 μm were adsorbed by m titania particles. <Preparation of surface uneven particles 8> Needle-like particles (graphite whiskers,
Nippon Graphite Co., Ltd. average diameter 0.1 μm, average length 10
70 g and silica with an average particle size of 0.01 μm (AEROSI
30 g of L MOX170 (manufactured by Nippon Aerosil Co., Ltd.) was compounded by a dry coagulation stirring method in which it was treated with a hybridizer at 16000 rpm for 5 minutes. <Creation of surface uneven particles 9> Needle-like particles (graphite whiskers,
Nippon Graphite Co., Ltd. average diameter 0.1 μm, average length 10
70m and titanium oxide with an average particle size of 0.01μm (ST
O1 (manufactured by Ishihara Sangyo Co., Ltd.) (30 g) was compounded by a dry coagulation stirring method in which it was treated with a hybridizer at 16000 rpm for 5 minutes. <Production of Organic Composite Particles 10> 70 g of acicular particles (graphite whiskers, manufactured by Nippon Graphite Co., Ltd., average diameter 0.1 μm, average length 10 μm) and zinc oxide (FINEX-50, Sakai Chemical Co., Ltd.) having an average particle size of 0.02 μm. 30 g of Kogyo Co., Ltd.) was compounded by a dry coagulation stirring method in which it was treated with a hybridizer at 16000 rpm for 5 minutes. <Preparation of Organic Composite Particles 11> 90 g of acicular particles (graphite whiskers, manufactured by Nippon Graphite Co., Ltd., average diameter 0.1 μm, average length 10 μm) and silica (A
EROSIL MOX170, Nippon Aerosil Co., Ltd. 10g,
Hybridization was performed at 16000 rpm for 5 minutes to form a composite by a dry coagulation stirring method. <Preparation of Organic Composite Particles 12> 50 g of needle-shaped particles (graphite whiskers, manufactured by Nippon Graphite Co., Ltd., average diameter 0.1 μm, average length 10 μm) and silica (A
EROSIL MOX170, manufactured by Nippon Aerosil Co., Ltd., 50 g,
Hybridization was performed at 16000 rpm for 5 minutes to form a composite by a dry coagulation stirring method.

The following composition was dispersed together with glass beads in a paint shaker (manufactured by Toyo Seiki Co., Ltd.) at room temperature for 20 minutes, and then the glass beads were filtered to obtain a dispersion.

Surface irregularity particles (described in Table 4) 100 g 10 wt% aqueous solution of gelatin (Wako Pure Chemical Industries, Ltd.) 300 g Tetraethoxysilane 30 g Ethanol 8.6 g Colloidal silica 20% aqueous solution (Snow Tech C, Nissan Chemical Industries Ltd. )) 182 g Fluorinated alkyl ester (FC-430, manufactured by 3M) 0.25 g Curing agent 1.0 g (CH ₂ = CHSO ₂ CH ₂ CONH (CH ₂ ) ₃ NHCOCH ₂ SO ₂ CH = CH ₂ ) 1 standard Hydrochloric acid 4g Water 150g

[0217]

[Table 4]

The above composition was coated on a support of ELP-2X type master (manufactured by Fuji Photo Film Co., Ltd.) using a wire bar so that the coating amount after drying was 6 g / m ^2.
An image-receiving layer was formed by heating at 0 ° C. for 5 minutes to prepare a lithographic printing plate precursor.

The Bekk smoothness of the surface of the obtained original plate is 60.
0 to 800 (sec / 10 mL), the contact angle with water was 5 degrees or less.

The lithographic printing plate precursor described above was replaced with “AM-Straight
Laser printer AMSIS 1200-J Plate using dry toner commercially available as "Imaging System"
Plate-making through Setter.

When the copied image of the obtained plate-making product was visually evaluated using a 20-fold loupe, the plate-making image quality was good.
That is, the plate-making product of the present invention obtained by dry toner transfer from a laser printer has no thin lines or thin characters, the solid part is uniform, no unevenness in toner transfer is recognized, and the non-image part is also not present. However, the background fog caused by the toner scattering was also slight, and it was good without any practical problems.

Next, the lithographic printing plate precursor was subjected to plate making by the same operation as described above, and then, using a fully automatic printing machine AM-2850 (manufactured by AM Co.), as fountain solution, a PS plate treating agent was prepared. EU-3
A solution obtained by diluting (manufactured by Fuji Photo Film Co., Ltd.) 50 times with distilled water was put in a dampening water tray part, and printing was performed using an ink ink for offset printing. The printed image (ground fog, solid uniformity in the image area) of the 10th printed matter was visually evaluated using a 20-fold magnifying glass, and it was extremely good.

Furthermore, 30,000 or more good printed matters were obtained which had an image without fine lines, loss of fine characters and uneven solid areas, and no ink stains on non-image areas.

The original plate of the present invention can produce a large number of good printed matters. Comparative Example 2 The surface irregularity particles of the image receiving layer composition had an average particle size of 0.4 μm.
A lithographic printing plate precursor was prepared in the same manner as in Example 47 except that m titanium oxide particles (rutile type, manufactured by Wako Pure Chemical Industries, Ltd.) were used.

The Beck smoothness of the surface of the obtained original plate is 60.
0 (second / 10 mL), the contact angle with water was 5 degrees or less.

The above original plate was prepared in the same manner as in Example 47. The image quality of the plate made was almost the same as that of Example 47, and the amount of scattered toner in the non-image area was small and the image was good.
However, when printing was performed in the same manner as in Example 47, the printed matter was found to have dusty stains in which the printing ink was slightly adhered to the non-image area from the printing. Further, when the image was printed as it was, and the image part was missing, about 1000 sheets were printed. Examples 57 to 68 <Preparation of Water-Resistant Support> A high-quality paper weighing 100 g / m ² was used as a substrate, a back layer coating composition having the following composition was applied to one surface of the substrate using a wire bar, and dried. Application amount 12
After providing the back layer of g / m ² , the smoothness of the back layer is 10
Calendar treatment was carried out so as to be about 0 (second / 10 mL) to obtain a water resistant support. (Paint for back layer) -Kaolin (50% aqueous dispersion) 200 parts-Polyvinyl alcohol aqueous solution (10%) 60 parts-SBR latex (solid content 50%, Tg: 0 ° C) 100 parts-Melamine resin (solid content 80 %, Sumirez resin SR-613) 5 parts Next, the other surface of the substrate is coated with an under layer coating composition having the following composition using a wire bar, and a dry coating amount of 10 g /
After providing the under layer of m ² , the smoothness of the under layer is 1500.
Calendar processing was performed so that the time would be about (sec / 10 mL). (Paint for under layer) -Carbon black (30% aqueous dispersion) 5.4 parts-Clay (50% aqueous dispersion) 54.6 parts-SBR latex (solid content 50%, Tg: 25 ° C) 36 parts- Melamine resin (solid content 80%, Sumirez resin SR-613) 4 parts The above components were mixed, and water was added so that the total solid content was 25% to obtain an under layer coating material.

The specific electric resistance value of the obtained under layer is
It measured as follows.

The under layer coating material was applied onto a stainless steel plate that had been thoroughly degreased and washed to obtain a coating film having a dry coating amount of 10 g / m ² . The specific electrical resistance of the obtained sample was measured by the three-terminal method with a guard electrode according to JIS K-6911, and a value of 4 × 10 ⁹ Ω · cm was obtained. <Preparation of direct-drawing lithographic printing plate precursor> The following composition, together with glass beads, is a paint shaker (manufactured by Toyo Seiki Co., Ltd.)
After being dispersed at room temperature for 20 minutes, the glass beads were filtered to obtain a dispersion.

[0229]   Surface uneven particles (listed in Table-5) 100 g   Polyvinyl alcohol (PVA117, Kuraray Co., Ltd.) 10% aqueous solution 100 g   Tetraethoxysilane 30g   Methyltrimethoxysilane 3g   Snow Tech C 20% aqueous solution 91g   Ethanol 10g   1N hydrochloric acid 5g   200 g of water

[0230]

[Table 5]

This dispersion was coated on the above water-resistant support with a wire bar so that the coating amount after drying was 6 g / m ² and dried in an oven at 100 ° C. for 20 minutes to prepare a lithographic printing plate precursor. It was created. <Preparation of oil-based ink (IK-2)> (Production example of resin particles) Poly (dodecyl methacrylate)
A mixed solution of 14 g, 30 g of methyl methacrylate, 66 g of methyl acrylate, 4.0 g of octadecyl methacrylate and 286 g of Isopar H was heated to 70 ° C. while stirring under a nitrogen stream. 2,2'-azobis (isovaleronitrile) as a polymerization initiator (abbreviation AI
VN) (1.5 g) was added, and the mixture was reacted for 4 hours. Furthermore, 2,
2'-azobis (isobutyronitrile) (abbreviation AIB
After adding 0.8 g of N.), the mixture was heated to a temperature of 80 ° C. and reacted for 2 hours, and subsequently 0.6 g of AIBN was added and reacted for 2 hours. Then, the temperature was raised to 100 ° C. and the mixture was stirred as it was for 1 hour to distill off unreacted monomers. After cooling, it was passed through a 200-mesh nylon cloth, and the obtained white dispersion was a latex having a polymerization rate of 93% and an average particle size of 0.35 μm.
The particle size was measured by CAPA-500 (manufactured by Horiba, Ltd.). (Preparation of ink) 10 g of dodecyl methacrylate / acrylic acid copolymer (copolymerization ratio: 98/2 weight ratio), 10 g of nigrosine and 30 g of Isopar H were put together with glass beads in a paint shaker (manufactured by Toyo Seiki Co., Ltd.) for 4 hours. Dispersion gave a fine black dispersion of nigrosine.

50 g (as solid content) of the above resin particles, 5 g (as solid content) of the above black dispersion and 0.06 g of cobalt dodecanoic acid salt were diluted to 1 liter of Isopar G to prepare a black oil-based ink (IK-2). )made.

[0233] The original plate obtained above can be used to draw a personal computer output.
00 is modified, the ink ejection head shown in FIG. 2 is attached to the pen plotter, and the above oil-based ink (IK
-2) was used for printing to make a plate. During plate making, the under layer provided directly below the image receiving layer of the printing plate and the counter electrode were electrically connected using a silver paste.

The plate thus prepared was adjusted to 10 by Ricoh Fuser (manufactured by Ricoh Co., Ltd.) adjusted so that the plate surface temperature became 70 ° C.
The ink image was fixed for a second.

The drawn image of the obtained plate-making product was observed and evaluated under an optical microscope at a magnification of 200 times. It was a clear image with no blurring or loss of fine lines or characters.

Next, the printing plate prepared as described above is
As a printing machine, Oliver 94 type (Sakurai Co., Ltd.) is used,
As a dampening water, a solution prepared by diluting EU-3 (manufactured by Fuji Photo Film Co., Ltd.) 100 times with distilled water was placed in a dampening water tray part, and printing was performed using an ink ink for offset printing.

[0237] The printed image of the 10th printed matter was visually evaluated with a magnifying glass of 20 times. As a result, no background stain was found on the non-image area due to the adhered printing ink, and the uniformity of the solid image area was good. there were. Even with a 200x optical microscope observation,
No fine lines or thin characters, no missing, etc. were observed, and the image quality was good.

30,000 or more printed matter having a print quality equivalent to this was obtained. Comparative Example 3 A lithographic printing plate precursor was prepared in the same manner as in Example 57 except that the surface irregularity particles of the image receiving layer composition were changed to silica particles having an average particle size of 2 μm (manufactured by Fuji Silysia, Sylysia).

The Bekk smoothness of the surface of the obtained plate is 600.
(Sec / 10 mL), the contact angle with water was 5 degrees or less.

The above plate was prepared in the same manner as in Example 57. The image quality of the plate made was almost the same as that of Example 57, and the amount of scattered toner in the non-image area was small and the image was good. However, when printing was carried out in the same manner as in Example 57, the missing of the printing portion occurred after printing about 1000 sheets. Example 69 Using the direct-drawing lithographic printing plate precursor prepared in Example 45, an ink-jet plate making machine using solid ink, which is commercially available as "SJ120 (Hitachi Koki Co., Ltd.)", is used for plate making. did.

When the copied image of the obtained plate-making product was visually evaluated with a 20-fold loupe, the plate-making image quality was good.
That is, the plate-making product of the present invention obtained from the solid inkjet plate-making machine is a fine line, there is no loss of fine characters, the solid part is uniform, and the non-image part is good without background fog due to ink scattering. there were.

Next, after making the lithographic printing plate precursor by the same operation as above, using a fully automatic printing machine AM-2850 (manufactured by AM Co., Ltd.), as a fountain solution, a PS plate treating agent was prepared. EU-3
A solution obtained by diluting (manufactured by Fuji Photo Film Co., Ltd.) 50 times with distilled water was put in a dampening water tray part, and printing was performed using an ink ink for offset printing. The printed image (ground fog, solid uniformity in the image area) of the 10th printed matter was visually evaluated using a 20-fold magnifying glass, and it was extremely good. Furthermore, 30,000 or more good prints were obtained which had an image without fine lines, missing fine characters and uneven solid areas, and free from ink stains on non-image areas.

The original plate of the present invention can produce a large number of good printed matters.

[0244]

By using the lithographic printing plate precursor of the present invention, it is possible to obtain an excellent image which does not cause spot stains as well as uniform stains on the entire surface. Furthermore, it is possible to print a large number of printed matter with clear images without image loss or distortion.

[Brief description of drawings]

FIG. 1 is a schematic configuration diagram showing an example of an apparatus system used for forming an image on a lithographic printing plate precursor according to the invention.

FIG. 2 is a schematic configuration diagram showing a main part of an inkjet recording apparatus used for forming an image on a lithographic printing plate precursor according to the invention.

FIG. 3 is a partial cross-sectional view of a head of an inkjet recording apparatus used for forming an image on a lithographic printing plate precursor according to the invention.

[Explanation of symbols]

1 Inkjet recording device 2 Master plate for lithographic printing 3 computer 4 bus 10 heads 10a discharge slit 10b Discharge electrode 10c counter electrode 11 oil-based ink 101 Upper unit 102 Lower unit

Claims (5)

[Claims] 1. A direct drawing type lithographic printing plate precursor having an image receiving layer on a water-resistant support, wherein the image receiving layer contains acicular particles having surface irregularities, and metal atoms and / or metalloid atoms. Direct drawing type, characterized by containing at least a binder resin composed of a resin containing a bond connected via an oxygen atom and an organic polymer containing a group capable of forming a hydrogen bond with the resin. Original for lithographic printing. 2. The acicular particles have an average diameter of 0.01 to 3 μm.
m, and the average length is 1 to 100 μm. 3. The direct drawing type lithographic printing plate precursor according to claim 1, wherein 3. The aspect ratio of the acicular particles (average length /
The direct drawing type lithographic printing plate precursor as claimed in claim 1 or 2, wherein the average diameter is 10 to 5,000. 4. The acicular particle having irregularities on the surface is a metal compound particle having photocatalytic properties, in which minute particles of a metal substance are carried on the surface, and the acicular particle is characterized in that: Direct drawing type lithographic printing plate. 5. Microparticles of a metal substance carried on the surface of a metal compound particle having photocatalytic property emit active light to the metal compound particle in the presence of a metal salt of the metal element having a smaller ionization tendency than hydrogen element. 5. A minute piece of the metal element deposited on the surface by irradiation, which is a minute piece.
Direct drawing type lithographic printing plate described.