JP2003019873A - 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 porous filler particles, and at least one type of metal alcoholate compound selected from the group consisting of a metal alcoholate represented by formulae Ti (OR<10> )4 and Al(OR<10> )3 , wherein R<10> is a 2-5C alkyl group), a chelate compound obtained by reacting the metal alcoholate with a β-diketone or the like and/or a β-keto-ester or the like and a partial hydrolysate obtained by reacting the chelate compound with water, a resin containing a bond for connecting a metal atom and/or a semi-metal atom via an oxygen atom, and a bonding resin made of a composite of the resin and an organic polymer containing 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 lithographic printing plate precursor for direct drawing and a method for producing the same, and more specifically, it provides a lithographic printing plate capable of printing a large number of printed matters with clear images free of background stains. Regarding the original plate for printing.

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

[0006] 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, a crosslinking catalyst for a silane coupling agent, and the like can be used in combination.

Further, as a binder used in the image receiving layer of the direct drawing type lithographic printing plate, 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. 1-226394 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 10 (1999) -58242). 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.

Particularly, in 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 print 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.

[0012]

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 type lithographic printing plate precursor that provides a printing plate that is capable of printing a large number of clear image-printed materials that are free from background stains and have no image defects or distortions. .

[0013]

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, porous filler particles, a general formula Ti (OR ¹⁰ ) ₄ and Al are contained in the image receiving layer.
A metal alcoholate represented by (OR ^{1 0} ) ₃ (in the formula, R ¹⁰ represents an alkyl group having 2 to 5 carbon atoms), and a metal alcoholate and β-diketones and / or β-ketoesters The chelate compound obtained by the reaction, and at least one metal alcoholate compound selected from the partial hydrolyzate obtained by reacting the chelate compound with water, and the metal atom and / or the semimetal atom, A direct drawing type lithographic printing plate characterized by containing at least a binder resin composed of a composite 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 plate for printing.

(2) A resin containing a bond in which a metal atom and / or a semimetal atom are connected via an oxygen atom is obtained by hydrolysis cocondensation of at least one compound represented by the following general formula (I). The lithographic printing plate precursor for direct drawing according to (1) above, which is a polymer that can be used.

The general formula (I) (R ⁰ ) _n M ⁰ (Y) _zn

[In the general formula (I), R ⁰ represents a hydrogen atom, a hydrocarbon group or a heterocyclic group, Y represents a reactive group,
M ⁰ represents a metal or metalloid having a valence of 3 to 6, z represents the valence of M ⁰ , and n represents ⁰ , 1, 2, 3 or 4. However, z
-N is 2 or more. ]

(3) The direct drawing type lithographic printing plate precursor as described in (1) or (2) above, wherein the average pore size distribution of the porous filler particles is 1Å to 1 μm.

[0019] (4) the average specific surface area of the porous filler particles is characterized by a ^{0.05m 2 / g~5000m 2 / g (} 1) a direct drawing type according to any one of the - (3) Original for lithographic printing.

(5) The mixing ratio of the binder resin and the total filler in the image receiving layer is as follows: binder resin / total filler = 80/20 to 5
/ 95 (mass ratio), wherein (1) to
The direct-drawing lithographic printing plate precursor as described in any of (4).

(6) Porous filler particles, Ti (OR ¹⁰ ) ₄ and Al (OR ¹⁰ ) _{3 of} the general formula (wherein R ¹⁰ represents an alkyl group having 2 to 5 carbon atoms) on a water resistant support. ), A chelate compound obtained by reacting the metal alcoholate with β-diketones and / or β-ketoesters, and partial hydrolysis obtained by reacting the chelate compound with water. At least one metal alcoholate compound selected from the group consisting of metal atoms and / or
Alternatively, a composition containing at least a compound in which a metalloid atom is bonded via an oxygen atom to form a resin, an organic polymer containing a group capable of forming a hydrogen bond with the resin, a hydrophilic organic solvent, and water is applied. A method for producing a direct drawing type lithographic printing plate precursor, which comprises drying to form an image receiving layer.

In the present invention, it is specified in the image receiving layer containing a binder resin comprising a composite of a resin containing a bond in which a metal atom and / or a semimetal atom are connected via an oxygen atom and an organic polymer. By containing the metal alcoholate compound, the stability of the coating solution at the time of coating the image receiving layer is improved, and sufficient hardening can be achieved under mild drying conditions. And by using the direct drawing type lithographic printing plate precursor thus obtained, it is possible to obtain an excellent image with an improved background stain, and moreover, a large number of clear printed images with no image loss or distortion. It becomes possible to print.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below. The porous filler particles used for the image receiving layer of the present invention will be described. The porous filler of the present invention may be inorganic particles or organic particles as long as it is porous and is not particularly limited. Examples of the inorganic porous filler include metals, oxides, complex oxides, hydroxides, carbonates, sulfates, silicates, phosphates, nitrides, carbides, sulfides, and composites of at least two of these. And the like, specifically, silica, glass, titanium oxide, zinc oxide, alumina,
Zirconium oxide, tin oxide, potassium titanate, aluminum borate, magnesium oxide, magnesium borate, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, basic magnesium sulfate, calcium carbonate, magnesium carbonate, calcium sulfate, magnesium sulfate, silicic acid Examples thereof include calcium, magnesium silicate, calcium phosphate, silicon nitride, titanium nitride, aluminum nitride, silicon carbide, titanium carbide, zinc sulfide, zeolite, and a compound of at least two or more thereof. Preferably,
Examples thereof include silica, glass, titanium oxide, alumina, zeolite, magnesium oxide, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium phosphate, calcium sulfate and the like.

Examples of the organic porous filler include carbon compounds, polymer compounds, celluloses, and composites of at least one of these compounds and an inorganic compound. Specifically, charcoal, activated carbon, polymer porous Examples thereof include sintered bodies, resin foams, silicon porous bodies, and super absorbent resins. Preferably, charcoal, activated carbon, polymer porous sintered body,
Superabsorbent resins and the like can be mentioned.

With respect to the size of the porous filler, the average particle diameter is preferably 0.03 μm to 20 μm, more preferably 0.05 μm to 15 μm, and further preferably 0.1 μm.
10 to 10 μm. The pore diameter of the porous filler has an average pore diameter distribution of preferably 1Å to 1 µm, more preferably 10Å to 500 nm, and further preferably 50Å to 300 n.
m. Surface area of the porous filler has an average specific surface area, preferably 0.05m ² / g~5000m ² / g, more preferably 1m ² / g~3000m ² / g, more preferably 10m ² / g~1000m ² / It is g.

In the present invention, it is not necessary that all the fillers used in the image receiving layer are porous fillers, and the amount of the porous filler is preferably 25% by mass or more of the total amount of fillers in the image receiving layer. , More preferably 50% by mass or more of the total amount of filler, and further preferably 75
It is at least mass%.

The filler that can be used in combination with the above-mentioned porous filler may be inorganic particles, organic particles, or a composite product thereof, and is 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 , ZnO, Fe ₂ O ₃ , ZrO ₂ ,
Particles of SnO ₂ , ZnS, CuS and the like can be mentioned. The organic particles include, for example, synthetic resin particles and natural polymer particles, preferably acrylic resin, polyethylene, polypropylene, polyethylene oxide, polypropylene oxide, polyethyleneimine, polystyrene, polyurethane, polyurea, polyester, polyamide, polyimide. , Carboxymethyl cellulose, gelatin, starch, chitin, chitosan and the like, more preferably resin particles of acrylic resin, polyethylene, polypropylene, polystyrene and the like.

The mixing ratio (mass ratio) of the composite (binder resin) and the total filler component is preferably 80/20 to 5/95, more preferably 70/30 to 5 in the binder resin / total filler.
/ 95, and more preferably 60/40 to 5/95.

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 General formula (I) (R ⁰ ).
_n M ⁰ (Y) _zn [In the general formula (I), R ⁰ represents a hydrogen atom, a hydrocarbon group or a heterocyclic group, Y represents a reactive group,
M ⁰ represents a metal or metalloid having a valence of 3 to 6, z represents the valence of M ⁰ , and n represents 0, 1, 2, 3, or 4. However,
z−n is 2 or more. 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, as a hetero ring, a pyran ring, a furan ring, a thiophene ring, 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 or 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 optionally substituted aromatic group having 6 to 12 carbon atoms (as the aromatic group, the aryl group in R ⁰ described 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 formula (I) include, but are not limited to, the followings.

Methyltrichlorosilane, methyltribromosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltrit-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). The specific bonding group preferably includes 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.

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, -N (R ²¹ ) CO is used as the repeating unit component.
^{-, - N (R 21)} 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 ²¹ 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 ^{twenty one}) CO-bonded
Is -N (R^{twenty one}) SO₂-Amide resin having a bond, -N
Ureido resin having HCONH-bond, -NHCOO
-Examples include urethane resins 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, for example, "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 amide bond-containing polymer include a polymer containing a repeating unit represented by the following general formula (II), an N-acylated polyalkyleneimine, or polyvinylpyrrolidone and its derivative.

[0049]

[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.

Regarding 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.

The N-acylated form of polyalkyleneimine is a carboxylic acid amide form containing -N (CO-R ²² )-which is obtained by a polymer reaction with a carboxylic acid halide, or a high-performance product with a sulfonyl halide. -N obtained by molecular reaction
A sulfonamide compound containing (SO ₂ —R ²² ) — (wherein
R ²² has the same meaning as R ²⁰ in the above formula (II).

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.

[0056]

[Chemical 2]

[0057]

[Chemical 3]

On the other hand, the hydroxyl group-containing organic polymer may be a natural water-soluble polymer, a semi-synthetic water-soluble polymer, or 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 the synthetic polymer include polyvinyl alcohol, polyalkylene glycol (polyethylene glycol, polypropylene glycol, (ethylene glycol / propylene glycol) copolymer, etc.), allyl alcohol copolymer, and acryl having 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 is preferable. 10/90 to 90/1 in ratio
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.

The binder resin containing the composite used in the present invention was produced by hydrolysis co-condensation of the compound (semi).
The hydroxyl group of the metal-containing resin and the specific bonding group in the organic polymer are uniform organic due to hydrogen bonding or the like,
It forms an inorganic hybrid and 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 complex used in the present invention is produced by hydrolyzing and cocondensing the above compound and mixing with an organic polymer, or by hydrolyzing and cocondensing the above compound in the presence of the organic polymer. To be done.

Preferably, the organic-inorganic polymer composite of the present invention can be obtained by hydrolyzing and cocondensing 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 oxide) produced by the hydrolytic cocondensation 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 a mixed solvent of water and a hydrophilic organic solvent, and examples of the hydrophilic organic solvent include 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 monoacetate, etc.), amides (formamide, N-methylformamide, pyrrolidone, N-methylpyrrolidone, etc.), and the like, You may use together 1 type (s) or 2 or more types.

In the present invention, a catalyst of the general formula Ti is used as a catalyst for promoting the hydrolysis and cocondensation reactions of the above compounds.
A metal alcoholate represented by (OR ¹⁰ ) ₄ and Al (OR ¹⁰ ) ₃ (in the formula, R ¹⁰ represents an alkyl group having 2 to 5 carbon atoms), the metal alcoholate and β-diketones, and / or At least one metal alcoholate compound selected from a chelate compound obtained by reaction with β-ketoesters and a partial hydrolyzate obtained by reacting the chelate compound with water is used.

Examples of the metal alcoholate compound include at least one metal alcoholate represented by the general formulas Ti (OR ¹⁰ ) ₄ and Al (OR ¹⁰ ) ₃ . R ¹⁰ in this metal alcoholate is, specifically, 2 to 5 carbon atoms.
Alkyl groups such as ethyl group, n-propyl group, i-
Examples include propyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group and the like. Specific examples of these metal alcoholates include tetra-i-propoxy titanium, tetra-n-butoxy titanium, tetrakis (2-ethylhexyloxy) titanium, tetrastearyloxy titanium, triethoxy aluminum, tri-i.
-Propoxy aluminum, mono-sec-butoxy-
Examples thereof include di-propoxy aluminum and tri-sec-butoxy aluminum.

Further, these metal alcoholates are, for example, β-diketones or β-ketoesters represented by the general formula R ¹¹ COCH ₂ COR ¹² (hereinafter, simply referred to as “β-diketones and / or β-ketoesters”. It is also possible to use as a chelate compound obtained by reacting the metal alcoholate with β-diketones and / or β-ketoesters to form a coordinate bond. R ¹¹ in the β-diketones and / or β-ketoesters is an alkyl group having 1 to 5 carbon atoms, for example, methyl group, ethyl group, n-propyl group, i-propyl group,
Examples thereof include an n-butyl group, a sec-butyl group, a t-butyl group, etc., and R ¹² is an alkyl group having 1 to 5 carbon atoms similar to R ^11, and an alkoxy group having 1 to 4 carbon atoms, for example, a methoxy group. , Ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, sec-butoxy group, t-butoxy group and the like.

Specific examples of the β-diketones and / or β-ketoesters include acetylacetone, methyl acetoacetate, ethyl acetoacetate, acetoacetic acid-n-
Propyl, acetoacetic acid-i-propyl, acetoacetic acid-n
-Butyl, acetoacetic acid-sec-butyl, acetoacetic acid-
t-butyl, 2,4-hexane-dione, 2,4-heptane-dione, 3,5-heptane-dione, 2,4-octane-dione, 2,4-nonane-dione, 5-methyl-hexane- Zion etc. can be mentioned. Of these, ethyl acetoacetate and acetylacetone are particularly preferable. These β-diketones and / or β-
The ketoesters may be used alone or in combination of two or more. This β-diketone and /
Alternatively, the β-ketoesters are the above-mentioned metal alcoholates 1
It is preferably used in a proportion of 0.8 to 5 mol, particularly preferably 1 to 3 mol, based on mol.

Specific examples of the chelate compound include ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate),
Aluminum monoacetylacetonate, bis (ethylacetoacetate), aluminum tris (acetylacetate), cyclic aluminum oxide isopropylate, di-i-propoxy bis (acetylacetonato) titanium and the like can be mentioned, and particularly ethylacetoacetate. Aluminum diisopropylate and aluminum tris (ethylacetoacetate) are preferred.

Further, these chelate compounds may be reacted with water to be used as a partial hydrolyzate. This water is preferably 0.1% with respect to 1 mol of the chelate compound.
It is used in a proportion of 8 to 3 mol, more preferably 1 to 2 mol. Among these catalysts, a chelate compound is preferable from the viewpoint of cocondensation property and storage stability of the obtained composition.

By using the catalyst of the present invention, the stability of the reaction solution and the hardenability are remarkably improved. For example, the stability of the reaction solution is improved 50 times or more under the condition of 35 ° C, and 100 ° C.
The hardenability can be improved three times or more under the dry conditions. The amount of the catalyst added is not particularly limited, but the metal atom and / or the semimetal in the compound in which the metal atom and / or the semimetal atom in the component can be bonded via the oxygen atom to form a resin. It is preferably 0.001 to 1 mol, and more preferably 0.01 to 1 mol with respect to 1 mol of the metal atom.
It is 0.5 mol.

Also, the compositions of the present invention can be cured faster.
Therefore, a curing accelerator may be used depending on the curing conditions.
In order to cure at relatively low temperature, a curing accelerator
It is more effective to use together. As this curing accelerator
Is naphthenic acid, octylic acid, nitrous acid, sulfurous acid, aluminum
Alkali metal salts such as acid and carbonic acid; sodium hydroxide,
Alkaline compounds such as potassium hydroxide; alkyl tita
Acid, phosphoric acid, p-toluenesulfonic acid, phthalic acid, etc.
Acidic compounds of ethylenediamine, hexanediamine,
Diethylenetriamine, triethylenetetramine, tet
Raethylene pentamine, piperidine, piperazine, meta
Phenylenediamine, ethanolamine, triethylamine
Min, γ-aminopropyltriethoxysilane, γ-
(2-Aminoethyl) -aminopropyltrimethoxyoxy
Orchid, γ- (2-aminoethyl) -aminopropylmethy
Ludimethoxysilane, γ-anilinopropyltrimethoxy
Amine compounds such as silane; (C_FourH₉)₂Sn (OCO
C₁₁H_{twenty three})₂, (C_FourH₉)₂Sn (OCOCH = CHCO
OCH₃)₂, (C_FourH₉)₂Sn (OCOCH = CHCOO
C_FourH ₉)₂, (C₈H₁₇)₂Sn (OCOC₁₁H_{twenty three})₂, (C
₈H₁₇)₂Sn (OCOCH = CHCOOCH₃)₂, (C₈
H₁₇)₂Sn (OCOCH = CHCOOC_FourH₉)₂, (C₈
H₁₇)₂Sn (OCOCH = CHCOOC₈H₁₇)₂, Sn
(OCOCC₈H₁₇)₂, (C_FourH₉)₂Sn (SCH₂CO
O), (C_FourH₉)₂Sn (SCH₂COOC₈H₁₇) ₂,
(C₈H₁₇)₂Sn (SCH₂COO), (C₈H₁₇)₂S
n (SCH₂CH₂COO), (C₈H₁₇)₂Sn (SCH₂
COOCH₂CH₂OCOCH₂S), (C₈H₁₇)₂Sn
(SCH₂COOCH₂CH₂CH₂CH₂OCOCH₂S),
(C₈H₁₇)₂Sn (SCH₂COOC₈H₁₇)₂, (C
₈H₁₇)₂Sn (SCH₂COOC₁₂H_{twenty five})₂Such as organic tin
Compound; (C_FourH₉)₂SnO, (C₈H₁₇)₂SnO, (C
_FourH₉) SnO, (C₈H₁₇) SnO and other organic tinctures
Side and ethyl silicate, ethyl silicate 40, ma
Dimethyl oleate, diethyl maleate, geophthalate
Comprised of reaction products with ester compounds such as octyl
Machine tin compounds are used. Of these curing accelerators
The ratio in the composition is 100 parts by mass of the solid content.
And usually 0.1 to 15 parts by mass, preferably 0.5 to 1
0 parts by mass is used.

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 image-receiving layer coating liquid on a water-resistant support using 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 Bekk 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 pass between the glass surface and the test piece under pressure reduction under reduced pressure.

When plate making (image formation) is carried out by an electrophotographic printer, the preferred range of toner to be used is dry toner and 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 the electrophotographic printer using the 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 200-2500 (sec / 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. In 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 to each other, resulting in strong image area. Can be held.

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, a zinc plate, a copper-aluminum plate, a copper-stainless plate,
Trimetal plates such as bimetal plates such as chrome-copper plates, chrome-copper-aluminum plates, chrome-lead-iron plates, chrome-copper-stainless plates, etc., with a thickness of 0.1-3 mm, especially 0.1-1 mm The following are listed. Also, the thickness is 80μ
Examples of the paper include water-resistant paper having a thickness of m to 200 μm, a plastic film, or a paper or 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 (sec / 10 m)
It is preferably adjusted to 1), 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 means a surface to which the image receiving layer is directly applied. For example, a conductive layer, an under layer and an over layer which will be described later are 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 whose surface state has been adjusted as described above is sufficiently retained without being affected by the irregularities on the surface of the support, and the image quality can be further improved.

As a method for setting the smoothness range, 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 specific electrical resistance value (also called volume specific electrical resistance value or specific electrical resistance value) is measured by 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 of 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.

The extrusion laminating method is preferable for laminating polyethylene resin mixed with carbon black. The extrusion laminating method is a method in which polyethylene is heat-melted to form a film, which is immediately pressed onto a base paper and then cooled and laminated, and various apparatuses are known. The thickness of the laminate layer is preferably 10 μm to 30 μm. When a plastic film or a metal plate having conductivity is used as the substrate, assuming that the entire support has conductivity, it can be used as it is if the water resistance is satisfied.

As the conductive plastic film, for example, polypropylene or polyester film mixed with a 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. As a water resistant substrate, the thickness is 80 μm to 2
Paper having a water resistance of 00 μm, a plastic film, a paper laminated with a metal foil, a 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 (sec / 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 film 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.

Plate-making is carried out by forming an image on the lithographic printing plate precursor of the present invention by a thermal transfer recording system, an electrophotographic recording system, an inkjet recording system or the like.

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 which is exposed based on 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 fixed by suction from the back surface by air suction. 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 excess developing solution, squeeze such as rubber roller, gap roller, reverse roller, etc., as shown on page 283 of the same document, corona squeeze, air squeeze, etc. are squeezed. 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 a lithographic printing plate precursor, which is a material to be transferred.
It is fixed, or 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, JP-A-61-211048 discloses that a hole is formed in a film-like ink support having a plurality of fine holes and ink is filled therein 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 inkjet recording apparatus 1 that 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 the 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 a digital signal of 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 ejection electrode 10b is preferably as narrow as possible in order to form a high quality image. For example, the head 10 of FIG. 3 is filled with oil-based ink, and the tip of the ejection electrode 10b having a width of 20 μm is used.
The distance between b and the counter electrode 10c is set to 1.5 mm, and a voltage of 3 kV is applied for 0.1 msec between the electrodes to obtain 40 μm.
Printing of m dots can be formed on the master 2.

As described above, on the lithographic printing plate precursor,
An image is formed by an inkjet method using an oil-based ink to obtain a plate making master.

[0130]

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 <Preparation of direct-drawing lithographic printing plate precursor> The following composition 1 was dispersed together with glass beads in a paint shaker (Toyo Seiki Co., Ltd.) at room temperature for 10 minutes, and then the following composition was further added. After 33 g of the substance 2 was added and dispersed for 1 minute at room temperature with a paint shaker (Toyo Seiki Co., Ltd.), glass beads were filtered to obtain a dispersion.

(Composition 1) Porous filler; Alumina RK30 (Iwatani Chemical Co., Ltd., average particle size 0.6 μm, average pore size 50 Å, average specific surface area 300 m ² / g) 31 g PVA 117 (Kuraray Co., Ltd.) ) 5 wt% aqueous solution 70 g Colloidal silica 20% aqueous solution; Snowtex C (Nissan Chemical Co., Ltd.) 60 g

[0133] (Composition 2)   Tetramethoxysilane 92g   Ethanol 163g   Water 163g   Aluminum acetylacetonate (manufactured by Wako Pure Chemical Industries, Ltd.) 11.5 g

Support for ELP-2X type master (manufactured by Fuji Photo Film Co., Ltd.) used as an electrophotographic lithographic printing original plate for light printing (Beck smoothness on the under side: 20)
00 (sec / 10 ml)) using a wire bar so that the coating amount after drying is 5 g / m ² , and drying in an oven at 100 ° C. for 2 minutes to obtain an image. An accepting layer was formed and used as a lithographic printing plate precursor.

The lithographic printing plate precursor was measured for its smoothness using a Beck's smoothness tester (produced by Kumagai Riko Co., Ltd.) under an air volume of 10 ml, and it was 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.

(Evaluation of Stability of Dispersion) The coating dispersion was treated at 50 ° C.
Stored under thermo conditions and visually evaluated the state of aggregation and gelation.

(Evaluation of Film Strength) In order to evaluate the surface of the prepared lithographic printing plate precursor, it was rubbed with a water-containing swab 10 times reciprocatingly, and the degree of surface damage was visually evaluated. ○: No film damage △: Surface change (film loss) ×;
Complete damage to the membrane

(Evaluation of background stain) Fully automatic printing machine AM-285
0 (trade name, manufactured by AM Co., Ltd.) as a fountain solution for treating PS plate EU-3 (Fuji Photo Film Co., Ltd.)
A solution prepared by diluting 50% by volume with distilled water was placed in a dampening water tray part, and printing was performed using black ink for offset printing. The printed image (ground fog, solid uniformity of image area) of the 10000th printed matter was visually evaluated using a loupe of 20 times.

(Evaluation of printing durability) “AM-Straight Imaging
Laser printer using dry toner commercially available as "System" AMSIS 1200-J Plate S
The plate was made through etter (trade name).

The copy image of the obtained plate-making product was visually evaluated with a 20-fold loupe, and 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. The background fog caused by the toner scattering was also slight, and it was good without any practical problems.

Next, printing was performed under the same conditions as the background stain evaluation method, and the number of printed lines, the thin lines, the loss of fine characters, and the number of irregularities in the solid portion were evaluated.

Comparative Example 1 For lithographic printing in the same manner as in Example 1 except that 11.5 g of aluminum acetylacetonate (manufactured by Wako Pure Chemical Industries, Ltd.) of the image receiving layer composition 2 was changed to 0.1 g of nitric acid. The original edition was created. The Bekk smoothness of the surface of the obtained original plate is 160.
(Sec / 10 ml), the contact angle with water was 5 degrees or less.

Comparative Example 2 A lithographic printing plate precursor was prepared in the same manner as in Example 1 except that 11.5 g of aluminum acetylacetonate (manufactured by Wako Pure Chemical Industries, Ltd.) of the image receiving layer composition 2 was changed to 1 g of phosphoric acid. Created. The Bekk smoothness of the surface of the obtained original plate is 140 degrees (s
ec / 10 ml), and the contact angle with water was 5 degrees or less.

Comparative Example 3 11.5 g of aluminum acetylacetonate (manufactured by Wako Pure Chemical Industries, Ltd.) of the image receiving layer composition 2 was added to ammonia water (2
A lithographic printing plate precursor was prepared in the same manner as in Example 1 except that the amount was changed to 0%). The Bekk smoothness of the surface of the obtained original plate was 155 degrees (sec / 10 ml), and the contact angle with water was 5 degrees or less.

[0145]

[Table 1]

In Example 1, the stability of the dispersion liquid and the film strength were good, and when it was used as a printing plate, there were 30,000 or more printed materials without scumming, without fine lines, fine characters missing, or uneven solid areas. Can be printed. On the other hand, in Comparative Examples 1 and 2, the stability of the dispersion liquid and the film strength are lowered, and further, during printing,
The image receiving layer is broken, and the background stain and printing durability are greatly reduced.
Further, in Comparative Example 3, the stability of the dispersion liquid and the film strength are greatly lowered, and accordingly, the image receiving layer is broken during printing, and the background stain and the printing durability are greatly lowered.

Example 2 <Preparation of lithographic printing plate precursor for direct drawing> The following composition 3 was dispersed with glass beads in a paint shaker (Toyo Seiki Co., Ltd.) at room temperature for 10 minutes, and then the following composition was further added. 33 g of the substance 4 was added and dispersed for 1 minute at room temperature with a paint shaker (Toyo Seiki Co., Ltd.), and then glass beads were filtered to obtain a dispersion.

(Composition 3) Porous filler: Aluminum hydroxide RH30 (Iwatani Chemical Co., Ltd., average particle size 1.5 μm, average pore size 100 Å, average specific surface area 50 m ² / g) 31 g PVA 117 (Kuraray Co., Ltd. )) 5 wt% aqueous solution 70 g Colloidal silica 20% aqueous solution; Snowtex C (Nissan Chemical Co., Ltd.) 60 g

[0149] (Composition 4)   Tetraethoxysilane 92g   Ethanol 163g   Water 163g   Ethyl acetoacetate aluminum diisopropylate   (Kawaken Fine Chemicals Co., Ltd.) 10g

Application amount 6 g / m after drying the above composition on a support of an ELP-2X type master using a wire bar.
Apply to ² and dry to the touch, then 110
A lithographic printing plate precursor was prepared by heating at ℃ for 30 minutes. The Bekk smoothness of the surface of the obtained original plate is 1000 (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.), 14.4 g of the following binder resin (P-1), and the following binder resin (P-2) 3 ．
A mixture of 6 g, 0.15 g of the following compound (A) and 80 g of cyclohexanone was put in a 500 ml glass container together with glass beads and dispersed with a paint shaker (manufactured by Toyo Seiki Seisakusho) for 60 minutes, and then the glass beads were separated by filtration to disperse the photosensitive layer. It was a liquid.

[0152]

[Chemical 4]

Next, this 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 produced as described above was corona-charged in the dark to have a surface potential of +450 V, which was then read from a document in advance by a color scanner 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, development was carried out using a liquid developer having the following contents, followed by rinsing in a bath of Isopar G alone to remove stains on the non-image area, and then with warm air at a surface temperature of the photoconductor of 50 ° C. It was dried so that the remaining amount of Isopar G was 10 mg / g of toner. 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> The components having the following composition were mixed in a kneader and kneaded at 95 ° 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 mass of this pulverized product and 4 parts by mass of Isopar H were dispersed for 6 hours with a paint shaker to obtain a dispersion. This dispersion is diluted with Isopar G so that the solid content of the toner is 1 g per liter, and at the same time 1 barium petrone is used as a charge control agent that imparts negative chargeability.
A liquid developer was prepared so as to contain 0.1 g per liter.

[0157] (Composition for kneading)     Ethylene / methacrylic acid copolymer 4 mass group     (Nucrel N-699 manufactured by Mitsui DuPont)     Carbon black # 30 (manufactured by Mitsubishi Kasei Co., Ltd.) 1 part by mass     Isopar L (manufactured by Exxon) 15 parts by mass

The lithographic printing plate precursor with the image formed thereon was heated at a temperature of 10
The toner image area was completely fixed by heating at 0 ° C. for 30 seconds. The drawn image of the obtained plate-making product was observed and evaluated 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 due to the adhered printing ink was found 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. 30,000 or more prints with print quality equivalent to this were obtained.

Example 3 <Preparation of Water-Resistant Support> A high-quality paper weighing 100 g / m ² was used as a substrate, and one surface of the substrate was coated with a back layer coating composition having the following composition using a wire bar. Dry coating amount 12g /
After providing the back layer of m ^2, the back layer has a smoothness of 100.
The calendar process was performed so that it was about (sec / 10 ml).

[0162] (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, an under layer coating composition having the following composition was applied to the other surface of the substrate using a wire bar to form an under layer having a dry coating amount of 10 g / m ² , and then the under layer had a smoothness of 1500. The calendar process was performed so that it was about (sec / 10 ml).

[0164] (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

By mixing the above components, the total solid content becomes 2
Water was added so as to be 5% 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 is applied to a stainless steel plate that has been thoroughly degreased and washed, and the dry coating amount is 10 g /
The coating film was 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 to obtain a value of 4 × 10 ⁹ Ω · cm.

The following composition 5 was dispersed with glass beads in a paint shaker (Toyo Seiki Co., Ltd.) at room temperature for 10 minutes, and 33 g of the following composition 6 was further added to the paint shaker (Toyo Seiki Co., Ltd.). )) At room temperature for 1 minute, and then the glass beads were filtered to obtain a dispersion.

(Composition 5) Porous filler: Magnesium hydroxide (Wako Pure Chemical Industries, Ltd., average particle size 0.6 μm, average pore size 200 Å, average specific surface area 100 m ² / g) 31 g PVA 117 (Kuraray Co., Ltd.) ) 5 wt% aqueous solution 70 g Colloidal silica 20% aqueous solution; Snowtex C (Nissan Chemical Co., Ltd.) 60 g

[0169] (Composition 6)   Tetraethoxysilane 92g   Ethanol 163g   Water 163g   Aluminum acetylacetonate (manufactured by Wako Pure Chemical Industries, Ltd.) 5g   Ethyl acetoacetate aluminum diisopropylate   (Kawaken Fine Chemicals Co., Ltd.) 10g

This dispersion was coated on the above waterproof substrate using a wire bar so that the coating amount after drying would be 6 g / m ^2, and dried in an oven at 100 ° C. for 20 minutes to print. The original edition was created.

<Preparation of Oil 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) Dodecyl methacrylate / acrylic acid copolymer (copolymerization ratio: 98/2 mass ratio) 1
0 g, 10 g of alkali blue and Shersol 71,
30 g together with glass beads was placed in a paint shaker (manufactured by Toyo Seiki Co., Ltd.) and dispersed for 4 hours to obtain a fine blue dispersion of alkali blue. 50 g of the above resin particles
A blue oil-based ink (IK-1) was prepared by diluting 5 g (solid content) of the above-mentioned blue dispersion and 0.06 g of zirconium naphthenate into 1 liter of Isopar G (as solid content).

[0173] 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 by the Ricoh Fuser (manufactured by Ricoh Co., Ltd.) adjusted to a plate surface temperature of 70 ° C.
The ink image was fixed by heating for 2 seconds. The image of the obtained plate-making product was observed and evaluated 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. 2 print images of the 10th print
When visually evaluated using a 0-fold magnifying glass, no background stain due to the adhesion of printing ink to the non-image area was observed, and the uniformity of the solid image area was good. Further, even when observed with an optical microscope at a magnification of 200 times, fine lines, thin characters, thinning, and the like were not observed, and the image quality was good. 30,000 or more prints with print quality equivalent to this were obtained.

Examples 4 to 12 As in Example 1, except that the compounds shown in Table 2 below were used instead of the aluminum acetylacetonate (manufactured by Wako Pure Chemical Industries, Ltd.) used as the catalyst. Similarly, a lithographic printing plate precursor was prepared.

[0177]

[Table 2]

The Bekk smoothness of the surface of each obtained master plate is 8
In the range of 00 to 1200 (sec / 10 ml), the contact angle with water was 5 degrees or less. When a printing plate was prepared by making in the same manner as in Example 1 and 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.

Examples 13 to 17 For lithographic printing in the same manner as in Example 1 except that the compounds shown in Table 3 below were used instead of the porous filler (alumina RK30) used as the filler. The original edition was created.

[0180]

[Table 3]

The Bekk smoothness of the surface of each obtained original plate is 8
In the range of 00 to 1200 (sec / 10 ml), the contact angle with water was 5 degrees or less. When a printing plate was prepared by making in the same manner as in Example 1 and 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.

Examples 18 to 31 In Example 3, the organic polymer PVA117 (Kuraray) was used.
Co., Ltd.) 5 wt% aqueous solution and silane compound In place of tetramethoxysilane, compounds shown in Table 4 below were used,
A lithographic printing plate precursor was prepared in the same manner as in Example 3.

[0183]

[Table 4]

The Beck smoothness of the surface of each obtained original plate is 8
In the range of 00 to 1200 (sec / 10 ml), the contact angle with water was 5 degrees or less. When a printing plate was prepared by making a plate in the same manner as in Example 3, and printing was performed, all of the obtained prints had clear image quality with no stains on the non-image areas, as with the prints of Example 3. The printing durability was as good as 30,000 sheets or more.

Example 32 An ink jet plate making machine using solid ink, which is commercially available as a solid ink jet plate maker SJ120 (Hitachi Koki Co., Ltd.), using the lithographic printing plate precursor for direct drawing prepared in Example 3 It was used for plate making. 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 from the solid inkjet plate-making machine,
There was no loss of fine characters, the solid part was uniform, and the non-image part was also good with no background fog due to ink scattering.

Next, after making the lithographic printing plate precursor by the same operation as described above, a fully automatic printing machine AM-2850 (manufactured by AM Co.) was used as fountain solution to prepare a PS plate treating agent. E
A solution obtained by diluting U-3 (manufactured by Fuji Photo Film Co., Ltd.) with distilled water 50 times was put in a dampening water tray part, and printing was performed using an ink for offset printing. 2 print images of the 10th printed matter (background fog, solid image uniformity)
When visually evaluated using a magnifying glass of 0 times, 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 matter.

[0187]

According to the present invention, the stability of the coating solution at the time of coating the image receiving layer is improved, and sufficient hardening can be achieved under mild drying conditions. Further, by using the direct drawing type 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

Continued front page    F-term (reference) 2C056 EA13 FA07 FC06                 2H114 AA04 AA27 BA10 DA26 DA28                       DA39 DA41 DA64 DA75 FA13                       GA34 GA38                 4J038 CG171 CK031 DG001 DH001                       DJ001 DJ011 DL021 DL041                       DL051 DL071 DL081 DL091                       DL101 DM021 HA066 HA146                       HA446 HA486 HA506 JB23                       JC38 KA08 KA22 NA05 PB14

Claims (6)

[Claims] 1. A direct drawing type lithographic printing plate precursor having an image receiving layer on a water-resistant support, wherein (1) is contained in the image receiving layer.
Porous filler particles, (2) a metal alcoholate represented by the general formula Ti (OR ¹⁰ ) ₄ and Al (OR ¹⁰ ) ₃ (wherein R ¹⁰ represents an alkyl group having 2 to 5 carbon atoms), Chelate compound obtained by reaction of metal alcoholate with β-diketones and / or β-ketoesters, and at least one selected from partial hydrolyzate obtained by reacting the chelate compound with water A metal alcoholate compound, and (3) 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. 2. A resin containing a bond in which a metal atom and / or a semimetal atom are connected via an oxygen atom is obtained by hydrolysis cocondensation of at least one compound represented by the following general formula (I). The direct-drawing lithographic printing plate precursor according to claim 1, which is a polymer. General formula (I) (R ⁰ ) _n M ⁰ (Y) _zn [In the general 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. ] 3. The lithographic printing plate precursor for direct drawing according to claim 1, wherein the average pore size distribution of the porous filler particles is 1Å to 1 μm. 4. A direct drawing type lithographic printing plate precursor according to claim 1, average specific surface area of the porous filler particles is characterized by a 0.05m ² / g~5000m ² / g . 5. The mixing ratio of the binder resin and the total filler in the image receiving layer is such that the binder resin / the total filler = 80/20 to 5/9.
It is 5 (mass ratio), The direct-drawing type planographic printing original plate in any one of Claims 1-4 characterized by the above-mentioned. 6. A water-resistant support having (1) porous filler particles, (2) general formulas Ti (OR ¹⁰ ) ₄ and Al (OR).
¹⁰ ) ₃ (in the formula, R ¹⁰ represents an alkyl group having 2 to 5 carbon atoms), obtained by a reaction of the metal alcoholate with β-diketones and / or β-ketoesters. Chelate compound, and at least one metal alcoholate compound selected from the partial hydrolyzate obtained by reacting the chelate compound with water,
(3) A compound in which a metal atom and / or a semimetal atom is bonded via an oxygen atom to form a resin, (4) an organic polymer containing a group capable of forming a hydrogen bond with the resin, (5)
A method for producing a direct drawing type lithographic printing plate precursor, which comprises applying a composition containing at least a hydrophilic organic solvent and (6) water and drying the composition to form an image receiving layer.