JP2002192847A - Original plate for planographic printing plate, printing method and printing press - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an orginal plate for a planographic printing plate capable of repeatedly performing printing having high sensitivity and excellent in plate wear and antisumming properties by the same printing press performing printing work by performing the formation of the original plate for the planographic printing plate and the making of a printing plate on the same printing press, a printing method and a printing press. SOLUTION: A process for forming a particle layer (image forming layer) 13 by applying an electric field across the hydrophilic support 11, which has a hydrophilic layer containing anatase type titanium fine particles, and high-molecular polymer fine particles having charge arranged on the plate cylinder 1 of the printing press to electrically deposit the high-molecular polymer fine particles on the support, a process for imagewise exposing the particle layer 13 and a process for performing printing after removing a non-image part by ink, water or rubbing and washing a plate surface by chemical or physical treatment after the completion of printing to remove the image on the plate surface and performing the irradiation of the plate surface with ultraviolet rays by an ultraviolet irradiation device 8 to regenerate the hydrophilic support 11 are provided.

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, a printing method using the lithographic printing plate precursor, and a printing press.
The present invention relates to a lithographic printing plate precursor capable of forming a printing plate precursor, making a printing plate, and repeatedly printing on the same printing machine with high sensitivity and excellent in printing durability and stain resistance, a printing method thereof, and a printing machine.

[0002]

2. Description of the Related Art In recent years, as a trend of lithographic printing technology, it has been proposed to produce a printing plate directly on the same printing press as that for performing a so-called printing operation by lithographic printing directly on a printing press. For example, on the surface of a conventional plate cylinder for offset printing, etc., those provided with a resin layer whose solubility in an aqueous solution changes by light or heat, those provided with a layer containing heat-fusible particles, light or Consideration or commercialization of those with a layer to be ablated by heat, those with an electrophotographic photosensitive member to form a lithographic printing plate image by an electrophotographic method, those that form a lithographic printing plate image by an inkjet recording method, etc. Have been. However, those provided with a resin layer whose solubility in alkaline water or the like is changed by light or heat are relatively expensive, harmful to the human body, and associated with flammability and other organic solvents. In addition, there is a problem that an apparatus for performing development processing with alkaline water or the like after image recording is required. Further, those provided with a layer containing the heat-fusible particles,
When the layer is provided, it is common to apply a dispersion of the particles in an aqueous dispersion medium, but a high-temperature operation is required to volatilize the aqueous dispersion medium after application, and an apparatus for the operation is required. Problem.

[0003] Further, a device provided with a layer that is ablated by light or heat is also used for forming the ablation layer.
There is a problem that an organic solvent that is relatively expensive, harmful to the human body, and involves dangers such as flammability is required. In the case where a toner image obtained on a photoconductive photoreceptor by electrophotography is transferred to a support to form a lithographic printing plate, charging,
Since a relatively large number of processes such as exposure and development with toner are required, there is a problem that the number of devices required for the processes is increased. Further, in the case of forming a lithographic printing plate image on a hydrophilic support by an ink jet recording method, there is a problem that an ink jet nozzle and a device for desensitizing a non-image portion are required. Further, Japanese Patent Application Laid-Open No. 10-58851 discloses a lithographic printing member manufacturing and apparatus in which image formation and printing of a printing member are performed by the same apparatus, and an aqueous base containing hydrophobic thermoplastic polymer particles and the like. A lithographic printing member in which a coating (thermosensitive layer) is provided on a hydrophilic support is shown. In such a method of forming an image by simply fusing hydrophobic thermoplastic polymer particles by heat and uniting, Although it shows good on-press developability, there is a problem that the stain resistance is insufficient, the water resistance and the image strength are weak, so that the printing durability is insufficient.

[0004]

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a lithographic printing plate precursor, a printing method and a printing machine which overcome the above-mentioned drawbacks of the prior art. That is, on the same printing press that performs the printing operation, the lithographic printing plate precursor is formed and the printing plate is made, and printing with high sensitivity, excellent printing durability and stain resistance can be repeatedly performed on the same printing press. An object of the present invention is to provide a lithographic printing plate precursor, a printing method thereof, and a printing machine. A further object of the present invention is that, for the formation of the image forming layer, an organic solvent that is relatively expensive, harmful to the human body, and involves a danger such as flammability is not required, and a process for forming a lithographic printing plate image is unnecessary. It is an object of the present invention to provide a printing method and a printing machine which have a high sensitivity and a high printing durability and can reduce the number of apparatuses for the processing.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies in order to achieve the above object, and as a result, using fine particles of charged polymer and containing fine particles of anatase type titanium oxide on a printing press. A photosensitive particle layer (image forming layer) is formed on a support having a hydrophilic layer by electrodeposition, and then an image is formed by laser light scanning exposure or the like. It is possible to print with excellent printing durability without printing stains.Also, there is no printing stains in repeated formation of a lithographic printing plate precursor and printing plate making, and printing with excellent printing durability can be achieved. They have found that they can do this and have accomplished the present invention. That is, the present invention is as follows.

(1) An electric field is applied between a charged polymer fine particle dispersion and a hydrophilic support having a hydrophilic layer containing anatase-type titanium oxide fine particles, so that the support is placed on the support. A lithographic printing plate precursor comprising an image forming layer containing electrodeposited high molecular weight polymer particles. (2) a hydrophilic support having a hydrophilic layer containing anatase-type titanium oxide fine particles set on a printing press plate cylinder, and a dispersion containing charged polymer fine particles in an electrically insulating liquid. Applying an electric field during the process to electrodeposit the polymer fine particles on the support to form an image-forming layer, exposing the image-forming layer to an image, non-image formation by ink, water or rubbing. A printing method comprising a step of performing printing after removing a part. (3) After being subjected to printing by the printing method, the image portion on the surface of the printing plate is subjected to plate cleaning by chemical treatment or physical treatment to remove the image of the plate, and is further irradiated with ultraviolet rays to be hydrophilic. The printing method according to claim 2, further comprising a step of regenerating the porous support. (4) A plate cylinder on which a hydrophilic support having a hydrophilic layer containing anatase-type titanium oxide fine particles is installed, and an electric field is applied between the hydrophilic support and the charged polymer fine particles to apply the electric field to the plate support. A printing machine comprising: a device for electrodepositing the high-molecular polymer fine particles on a support to form a particle layer; a drawing device having an exposure light source; a plate surface cleaning device; and an ultraviolet irradiation device.

The lithographic printing plate precursor, the printing method and the printing machine of the present invention are, specifically, a liquid developer (toner) for electrophotography.
Is used as a dispersion of charged polymer fine particles, and is electrodeposited on the hydrophilic support provided on a plate cylinder on a printing press to form a photosensitive particle layer (image forming layer). Form a negative image on the substrate by thermal fusion of the particles in the exposed area,
The unexposed part is a method of printing by removing it with dampening water or ink on a printing press, and after printing, regenerate the printing plate by wiping the plate surface cleaner, electrodepositing again and repeating, printing by the above operation And a direct imaging system including a printing machine for the method.

One of the features of the lithographic printing plate precursor according to the present invention is that the high molecular polymer in which the particle layer (image forming layer) on the hydrophilic support on the printing plate cylinder is charged as described above. It consists of a layer in which the fine particles are electrodeposited on a hydrophilic support by applying an electric field between the fine particle dispersion and the support.

The features and merits of using the above-mentioned high molecular weight polymer fine particles as charged fine particles are listed below. (1) The dispersion stability of the dispersion is good and the production can be stabilized. (2) By using charged particles, they can adhere to the substrate under an electric field (a high-precision coating device is unnecessary). (3) By electrodeposition, it adheres more firmly to the substrate than mere application. (4) Due to electrodeposition, the particles have an interaction between the particles rather than a mere coating, and a contact state is generated, so that the heat fusion efficiency is large, and the unexposed portions are also removed collectively, so that the on-press developability is excellent. . (5) It is observed that the particles have a three-dimensional structure in which the particles are stacked on the substrate, and that the particles are fused and maintain the three-dimensional structure even after exposure, so that the surface area of the exposed portion is increased and the ink is exposed. It is advantageous for acceptability. (6) In addition, since the polymer fine particles are dispersed in an electrically insulating liquid (non-aqueous solvent), and there is no need for a water-soluble resin, the image has excellent water resistance.

The dispersion medium of the polymer fine particle dispersion liquid is an electrically insulating liquid (non-aqueous solvent), and mainly uses an isoparaffinic petroleum solvent. It has no flammability problem, is safe in disaster prevention, and has a lower boiling point than the aqueous dispersion medium, so that it is advantageous for natural drying during the formation of the particle layer (image forming layer). For the formation of the image forming layer, a relatively expensive organic solvent that is usually required and is harmful to the human body and involves a danger of flammability is unnecessary in the printing method and the printing press of the present invention, and the lithographic printing plate image The number of processes for the formation is reduced, and the number of apparatuses for the process can be reduced.

Another feature of the lithographic printing plate precursor of the present invention is that
It has a hydrophilic layer containing anatase type titanium oxide fine particles as a support. When using an aluminum substrate that has been subjected to normal surface hydrophilic treatment,
The mere chemical treatment or physical treatment such as wiping with a cleaner may not sufficiently recover the hydrophilicity, may cause unevenness in the hydrophilicity, and may cause stains on the printed matter. In addition, when used repeatedly, dirt may gradually become noticeable. The lithographic printing plate precursor, the printing method, and the printing press of the present invention can be used in a normal printing process by providing, as a hydrophilic support, a hydrophilic layer containing anatase-type titanium oxide fine particles having a photocatalytic function on the support. After printing is completed, the plate is washed by chemical and / or physical treatment to remove the image on the plate, and the hydrophilic support can be regenerated by further irradiating ultraviolet rays,
Even when used repeatedly, it is possible to obtain a printed matter free of stains. The anatase-type titanium oxide fine particles used in the present invention are photo-excited by irradiation with ultraviolet light, and the surface of the particles is hydrophilized to have a photocatalytic function. By irradiating ultraviolet rays to the plate surface washing step, it is possible to oxidatively decompose the dirt components remaining on the plate surface after the cleaner and completely recover the hydrophilicity of the surface of the support. Therefore, even if used repeatedly, it is possible to obtain a printed matter free of stains.

The printing press of the present invention is provided with a plate surface cleaning device (cleaning unit) in the vicinity of the cylindrical plate cylinder. Between one printing operation and the next printing operation, ink attached to the surface of the plate (hydrophilic support) after printing is completed;
Or, after wiping the dampening solution, etc., the chemical treatment and / or
Alternatively, the toner image portion adhered and fixed to the plate surface by physical processing can be removed.

As described above, the image forming layer is composed mainly of uniform high molecular weight polymer particles, and since the high molecular weight polymer particles are electrodeposited on the support, the fine particles contact each other as compared with coating. It exists in a semi-adhered state with voids.
Therefore, in the image formation by heat fusion of the fine particles by scanning exposure such as laser light in the infrared region, the heat-fusibility of the high-molecular polymer fine particles is good, strong image strength is obtained, and the unexposed portion In the non-image area, the fine particles are removed as a group to a certain extent, so that the fine particles have good removability, that is, they have good developability, and can be removed by a fountain solution or ink on a printing machine, and there is no print stain. Lithographic printing with excellent printing durability is possible. The printing method and printing press of the present invention, by electrodeposition formation of the image forming layer on the printing press, image exposure,
A Computer To Cylinder (CTC) printing method that eliminates the process of plate making can be realized. A lot of time and cost required for the production of a normal PS plate is not required, and a low-priced, short-term printed matter can be produced. In addition, plate exchange work after printing is not required, plate waste is not generated, and time, labor and cost can be reduced.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a lithographic printing plate precursor, a printing method and a printing machine according to the present invention will be described in detail. The lithographic printing plate precursor according to the present invention is, as described above, a dispersion liquid containing at least a charged polymer particle, a photothermal conversion agent and a charge control agent in an electrically insulating liquid, and anatase type titanium oxide particles. An electric field is applied between the support and a hydrophilic support having a hydrophilic layer, and an image forming layer on which the polymer fine particles are electrodeposited is provided on the support.

First, anatase-type titanium oxide fine particles which are contained in a hydrophilic layer formed on a hydrophilic support described later of the lithographic printing plate precursor according to the present invention and are one of the characteristic components in the present invention, and The hydrophilic layer will be described. The anatase-type titanium oxide fine particles used in the present invention are characterized in that they are photoexcited by irradiation with ultraviolet light, and the surface of the particles is hydrophilized. For details of the phenomenon that the surface is converted to hydrophilic by light irradiation, see, for example, Toshiya Watanabe, Ceramics, 31, 837
(1996). However, no application to a lithographic printing plate support has been disclosed.

As described above, the titanium oxide particles used in the present invention are characterized in that the crystal form is an anatase type and the surface of the particles is made hydrophilic by photoexcitation upon irradiation with ultraviolet light. The average particle size of the anatase type titanium oxide particles is 5 to 5
00 nm is preferable, and more preferably 5 to 100 nm.
It is. Within this range, the surface is made more hydrophilic by irradiation with ultraviolet light.

The anatase type titanium oxide particles are commercially available as a powder or as a titania sol dispersion. For example, Ishihara Sangyo Co., Ltd., Titanium Industry Co., Ltd.
Commercially available from Sakai Chemical Co., Ltd., Nippon Aerosil Co., Ltd., Nissan Chemical Industry Co., Ltd., etc. The anatase type titanium oxide particles used in the present invention may contain another metal element or an oxide thereof. The inclusion includes coating, supporting, or doping on the surface and / or inside of the particles.

As the metal element contained, for example, S
i, Mg, V, Mn, Fe, Sn, Ni, Mo, Ru,
Rh, Re, Os, Cr, Sb, In, Ir, Ta, N
b, Cs, Pd, Pt, Au and the like. Specifically, JP-A-7-228738 and JP-A-7-187677
Nos. 8-81223, 8-257399, 8
No. -283022, No. 9-25123, No. 9-714
No. 37, No. 9-70532. The content of these other metal elements or oxides thereof is preferably 10% or less, more preferably 5% or less, based on the total weight of the anatase type titanium oxide particles.

The hydrophilic layer may contain, as another component, inorganic pigment particles other than the anatase type titanium oxide particles of the present invention. For example, silica, alumina, kaolin, clay, zinc oxide, calcium carbonate, barium carbonate, calcium sulfate, barium sulfate, magnesium carbonate, titanium oxide other than anatase type crystals and the like can be mentioned. These other inorganic pigments are the anatase type titanium oxide particles 10 of the present invention.
It is used in an amount not exceeding 40 parts by weight with respect to 0 parts by weight. Preferably, it is within 30 parts by weight.

The resin provided to the hydrophilic layer of the present invention is a resin containing a resin having a bond of a siloxane component represented by the following general formula (I) as a main component.

[0021]

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More specifically, the siloxane bond represented by the general formula (I) contains the following bonds, and one or more of these bonds are present in the resin.

[0023]

Embedded image

Here, R ^{01 to} R ⁰³ may be the same or different and represent a hydrogen atom, a hydrocarbon group or a heterocyclic group.
The hydrocarbon groups and heterocyclic groups represented by A, B, R ⁰¹ , R ⁰² and R ⁰³ are the same as those represented by R ⁰ in the following formula (II).

Preferably, the hydrophilic layer is formed by a sol-gel method from a dispersion containing anatase type titanium oxide particles and at least one silane compound represented by the following general formula (II).

Formula (II) (R ⁰ ) _n Si (Y) _4-n [In the formula (II), R ⁰ represents a hydrogen atom, a hydrocarbon group or a heterocyclic group. Y is a hydrogen atom, a halogen atom, -OR
¹ , —OCOR ² or —N (R ³ ) (R ⁴ ) (R ¹ and R ² each represent a hydrocarbon group; R ³ and R ⁴ may be the same or different; Or a hydrocarbon group). n represents 0, 1, 2 or 3. ]

Preferably, R ⁰ in the general formula (II) is a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms which may be substituted, for example, a methyl group, an ethyl group, a propyl group. Group, butyl group, pentyl group, hexyl group,
A heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, and the like; examples of a group substituted by these groups include a halogen atom (a chlorine atom, a fluorine atom, and a bromine atom), a hydroxy group, a thiol group, a carboxy group, and a sulfo group. Group, cyano group,
Epoxy group, -OR 'group (R' is a hydrocarbon group, for example,
Methyl, ethyl, propyl, butyl, heptyl, hexyl, octyl, decyl, propenyl, butenyl, hexenyl, octenyl, 2-hydroxyethyl, 3-chloropropyl, 2- Cyanoethyl group, N, N-dimethylaminoethyl group, 2-bromoethyl group, 2- (2-methoxyethyl) oxyethyl group, 2-methoxycarbonylethyl group, 3-carboxypropyl group, benzyl group, etc.), -OCOR ′ Group,
-COOR 'group, -COR' group, -N (R ") (R")
(R ″ represents a hydrogen atom or the same content as R ′,
Each may be the same or different), -NHCONHR '
Group, -NHCOOR 'group, -Si (R') 3 group, -CON
HR "group, -NHCOR 'group and the like. These substituents may be substituted plurally in the alkyl group.

A linear or branched alkenyl group having 2 to 12 carbon atoms which may be substituted (for example, vinyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, octenyl group, decenyl group, dodecenyl group and the like) As the group substituted by these groups, those having the same contents as the groups substituted by the alkyl group may be mentioned, or a plurality of groups may be substituted), or a group having 7 to 14 carbon atoms may be substituted. An aralkyl group (for example, a benzyl group, a phenethyl group, a 3-phenylpropyl group, a naphthylmethyl group, a 2-naphthylethyl group, etc .; the groups substituted by these groups are the same as the groups substituted by the alkyl group. And alicyclic groups having 5 to 10 carbon atoms which may be substituted (for example, cyclopentyl group, cyclohexyl group, 2-cycloalkyl) Hexylethyl group, 2-cyclopentylethyl group, norbornyl group, adamantyl group, and the like, as the group substituted with these groups, those having the same contents as the substituents of the alkyl group may be mentioned. Good), an aryl group having 6 to 12 carbon atoms which may be substituted (for example, a phenyl group or a naphthyl group, examples of the substituent include those having the same content as the group substituted by the alkyl group. May be substituted), or a nitrogen atom,
A condensable heterocyclic group containing at least one atom selected from an oxygen atom and a sulfur atom (for example, the heterocycle includes a pyran ring, a furan ring, a thiophene ring, a morpholine ring, a pyrrole ring, a thiazole ring Oxazole ring, pyridine ring, piperidine ring, pyrrolidone ring, benzothiazole ring, benzoxazole ring, quinoline ring, tetrahydrofuran ring, etc., which may contain a substituent. And the same content may be mentioned, and a plurality may be substituted).

Preferably, Y is a halogen atom (representing a fluorine, chlorine, bromine or iodine atom), --O
R ¹ , —OCOR ² or —N (R ³ ) (R ⁴ ).
In the —OR ¹ group, R ¹ is an optionally substituted aliphatic group having 1 to 10 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, a butoxy group, a heptyl group, a hexyl group, a pentyl group, an octyl group, Nonyl group, decyl group, propenyl group,
Butenyl, heptenyl, hexenyl, octenyl, decenyl, 2-hydroxyethyl, 2-hydroxypropyl, 2-methoxyethyl, 2- (methoxyethyloxy) ethyl, 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, etc.).

In the —OCOR ² group, R ² is an aliphatic group having the same contents as R ¹ or an aromatic group having 6 to 12 carbon atoms which may be substituted (aromatic groups in the above R ⁰ And the same as those exemplified for the aryl group). In the —N (R ³ ) (R ⁴ ) group, R ³ and R ⁴ may be the same or different from each other.
10 to 10 aliphatic groups which may be substituted (for example,-
OR ^{1 having} the same content as R ¹ ). More preferably, the total number of carbon atoms of R ³ and R ⁴ is 16 or less.

Specific examples of the silane compound represented by the general formula (II) include, but are not limited to, the following. Methyltrichlorosilane, methyltribromosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltri-t-butoxysilane, ethyltrichlorosilane, ethyltribromosilane, ethyltrimethoxysilane, ethyltriethoxysilane, 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-decyltribromo Silane, n
-Decyltrimethoxysilane, n-decyltriethoxysilane, n-decyltriisopropoxysilane, n-decyltri-t-butoxysilane, n-octadecyltrichlorosilane, n-octadecyltribromosilane, n-
Octadecyltrimethoxysilane, n-octadecyltriethoxysilane, n-octadecyltriisopropoxysilane, n-octadecyltri-t-butoxysilane,
Phenyltrichlorosilane, 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, vinyltri-t-butoxysilane, Trifluoropropyltrichlorosilane, trifluoropropyltribromosilane, trifluoropropyltrimethoxysila , 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-aminopropyltri-t-butoxysilane, γ-mercaptopropylmethyldimethoxysilane ,
γ-mercaptopropylmethyldiethoxysilane, γ-
Mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyltriisopropoxysilane, γ-mercaptopropyltri-t-butoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4
-Epoxycyclohexyl) ethyltriethoxysilane, and the like.

The general formula (I) used for forming the hydrophilic layer of the present invention
Along with the silane compound represented by I), Ti, Zn, S
Gold that can be formed by sol-gel method of n, Zr, Al, Ni, etc.
Genus compounds can be used in combination. Metal compound used
As an object, for example, Ti (OR ^Five)_Four(R^FiveIs a methyl group, d
Tyl, propyl, butyl, pentyl, hexyl
Group), TiCl_Four, Zn (OR^Five)_Two, Zn (CH_ThreeCO
CHCOCH_Three)_Two, Sn (OR^Five)_Four, Sn (CH_ThreeCOC
HCOCH_Three)_Four, Sn (OCOR^Five)_Four, SnCl^Four, Zr
(OR^Five)_Four, Zr (CH_ThreeCOCHCOCH_Three)_Four, Al
(OR^Five)_Three, Ni (CH_ThreeCOO)_FourAnd the like.

The metal compound used in combination is used in a range where the uniformity, strength and the like of the film formed by the sol-gel method are sufficiently maintained. In the hydrophilic layer of the present invention, the proportion of the anatase type titanium oxide fine particles and the resin containing a siloxane bond is preferably 30 to 95/70 to 5 weight ratio. More preferably, the weight ratio is 50 to 80/50 to 20. Within this range, the strength of the film of the hydrophilic layer, the hydrophilicity of the surface after irradiation with ultraviolet light, and the like are well maintained, and a large number of clear images without background stain can be printed.

The hydrophilic layer of the present invention is preferably prepared by a sol-gel method, which can be performed by a conventionally known sol-gel method. Specifically, Saio Sakuhana, "Sol-Gel Science", Agne Shofusha Co., Ltd. (published)
(1988), Takashi Hirashima, "Functional thin film production technology by latest sol-gel method", General Technology Center (published) (1992)
It can be created according to the method described in detail in a written document such as year).

The coating liquid for the hydrophilic layer is an aqueous solvent, and a water-soluble solvent is used in combination for the purpose of uniform liquefaction by suppressing precipitation during preparation of the coating liquid. Examples of the water-soluble 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 monomethyl monoacetate, etc.), amides (formamide, N-methylformamide, pyrrolidone, N-methylpyrrolidone, etc.), and the like. You may use together.

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

The type of the acidic catalyst or the basic catalyst is not particularly limited, but when it is necessary to use a catalyst having a high concentration, a catalyst composed of an element such that the catalyst hardly remains in the crystal particles after sintering. Is good. In particular,
Examples of the acidic catalyst include hydrogen halide such as hydrochloric acid, nitric acid,
Sulfuric acid, sulfurous acid, hydrogen sulfide, perchloric acid, hydrogen peroxide, carbonic acid, carboxylic acids such as formic acid and acetic acid, substituted carboxylic acids in which R of the structural formula RCOOH is substituted by other elements or substituents, and sulfonic acids such as benzenesulfonic acid As the basic catalyst, ammonia bases such as aqueous ammonia,
Examples thereof include amines such as ethylamine and aniline.

The coating solution thus prepared is applied to a support by using any of the conventionally known coating methods.
Dry and form a film. The thickness of the formed hydrophilic layer is 0.2
10 to 10 μm, more preferably 0.5 to 8 μm
It is. In this range, a film having a uniform thickness is formed, and the film has sufficient strength.

The present invention also provides a film having a hydrophilic layer and a uniform TiO particle by utilizing the above resin having a siloxane bond, in particular, by forming a film using a sol-gel method. There is an advantage of being excellent in dispersibility. The titanium oxide-containing hydrophilic layer of the present invention exhibits hydrophilicity when exposed to light under ordinary handling conditions after coating and forming on a support, but adsorbs trace amounts of organic substances and the like in the air. For this reason, since hydrophilicity may be insufficient, it is preferable to mount the substrate on a printing press and then irradiate ultraviolet rays before electrodeposition of the toner to increase the hydrophilicity and make the film uniform. In the present invention, in order to effectively utilize the effect of the anatase type titanium oxide fine particles, the hydrophilic layer component preferably contains 30 to 95 wt% of titanium oxide fine particles, and more preferably 50 to 80 wt%. By containing the titanium oxide fine particles, the surface of the hydrophilic layer is covered with a sufficient titanium oxide surface, so that the desired hydrophilicity can be obtained. 3
If it is less than 0 wt%, the hydrophilicity of the hydrophilic surface is not always sufficient, and if it exceeds 95 wt%, the film properties tend to be ragged.

[Polymer Fine Particle Dispersion Having Charge] Next, the charge used for forming the image forming layer, which is another characteristic element of the lithographic printing plate precursor, the printing method and the printing machine of the present invention. A high-molecular polymer fine particle dispersion (also referred to as a toner) having the following will be described. The polymer fine particle dispersion of the present invention contains at least a polymer, a charge control agent, a dispersant, and a photothermal conversion agent.

(Polymer) Polymer (Coating agent)
As the resin, a thermoplastic resin that is insoluble or swells in the carrier liquid is used. These resins have an effect of adhering to the light-to-heat conversion agent or forming a coating film around the light-to-heat conversion agent to promote dispersion of the light-to-heat conversion agent, and an effect of improving fixability. As the resin, butadiene rubber, styrene-butadiene rubber, rubbers such as cyclized rubber, styrene resin, vinyltoluene resin, acrylic resin, methacrylic resin,
And copolymer resins thereof, polyester resins, polycarbonate resins, polyvinyl acetate resins, and various alkyd resins. Of these, acrylic resins, methacrylic resins and copolymer resins thereof are preferably used. The reason is that these resins can easily change the softening point or change the solubility in the carrier liquid by changing the alkyl chain length of the ester group.

(Charge Control Agent) As the charge control agent, conventionally known charge control agents can be used. For example, metal salts of fatty acids such as naphthenic acid, octenoic acid, oleic acid, and stearic acid, metal salts of sulfosuccinates, and JP-B-45-5-5.
No. 56, JP-A-52-37435, JP-A-5-37435
Oil-soluble sulfonic acid metal salts disclosed in JP-B-2-37049, metal phosphate salts described in JP-B-45-9594, and abieticin disclosed in JP-B-48-25666. Metal salts of acid or hydrogenated abietic acid, Ca salts of alkylbenzene sulfonic acid disclosed in JP-B-55-2620,
JP-A-2-107837, JP-A-52-38937, JP-A-57-90643, JP-A-57-13
No. 9753, etc., metal salts of aromatic carboxylic acids or sulfonic acids, nonionic surfactants such as polyoxyethylated alkylamines, oils and fats such as lecithin and linseed oil, polyvinylpyrrolidone, polyvalent Organic acid esters of alcohols, phosphate ester surfactants described in JP-A-57-210345, sulfonic acid resins described in JP-B-56-24944, and the like can be used. Also, JP-A-60-2105
No. 6, JP-A-61-50951 can also be used. The amino acid derivative is a compound represented by the following general formula (3) or (4) or a reaction mixture obtained by further reacting a reaction mixture obtained by reacting an amino acid with a titanium compound in an organic solvent with water. .

[0045]

Embedded image

(Wherein R ₁ and R ₂ are a hydrogen atom and have 1 to 1 carbon atoms)
Up to 22 alkyl groups, substituted alkyl groups (dialkylamino groups, alkyloxy groups, alkylthio groups as substituents), aryl groups having 6 to 24 carbon atoms, substituted aryl groups (dialkylamino groups, alkyloxy groups as substituents) Group, alkylthio group, chloro group, bromo group, cyano group, nitro group, hydroxyl group), aralkyl group, acyl group having 1 to 22 carbon atoms, alkylsulfonyl group, alkylphosphonyl group or 6 to 24 carbon atoms. An arylsulfonyl group and an arylsulfonyl group are shown. R ₁ , R ₂
May be the same or different, and may form a ring with R ₁ -R ₂ , but are not simultaneously hydrogen atoms. A represents an alkylene group having 1 to 10 carbon atoms or a substituted alkylene group. X represents a hydrogen atom, a monovalent to tetravalent metal, or a quaternary ammonium cation. n shows a positive integer. )

Of these, preferred are metal salts of naphthenic acid, metal salts of dioctylsulfosuccinic acid,
Lecithin and the aforementioned amino acid derivatives can be mentioned.
More preferred examples include zirconium, cobalt, and manganese salts of naphthenic acid, calcium and sodium salts of dioctylsulfosuccinic acid, and metal salts of the compound of the general formula (3). As the metal salt of the compound of the general formula (3), a salt of titanium, cobalt, zirconium or nickel is particularly preferred. As these charge control agents, two or more compounds can be used in combination.

(Dispersant) A dispersant is a resin that enhances the dispersibility of charged polymer fine particles (also referred to as toner). The dispersant dissolves or swells in a carrier liquid to thereby disperse the toner. Is a kind of resin. For example, rubbers such as styrene-butadiene, vinyltoluene-butadiene, and butadiene-isoprene; acrylic monomers having a long-chain alkyl group such as 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate; Polymers, and copolymers thereof with other monomers (styrene, (meth) acrylic acid and its methyl, ethyl, propyl esters, etc.)
Further, a graft copolymer and a block copolymer can be used. Among these preferred dispersants, a synthetic rubber-based dispersant is effective, and a random or block copolymer of a styrene-butadiene copolymer can be used as an extremely effective dispersant.

(Photothermal Conversion Agent) In the printing method of the present invention, when an image is formed by scanning exposure with a laser beam or the like, the polymer is used to convert light energy into heat energy in the polymer fine particle dispersion. It is preferable to include a photothermal conversion agent. As the photothermal conversion agent that may be contained, any substance that can convert light into heat by absorbing light such as ultraviolet light, visible light, infrared light, and white light can be used.For example, pigments, carbon black, metal colloids, titanium Black, metal carbide, boride, nitride, carbonitride powder and the like. Particularly preferred is a wavelength 760
a dye that effectively absorbs infrared rays from nm to 1200 nm,
Pigment, metal powder, metal compound powder. The photothermal conversion agent coated with the polymer can be used as the charged polymer fine particles. In that case, the photothermal conversion agent is preferably carbon black or the like.

[Production Method of Particles] First, the resin as the coating agent and the light-to-heat conversion agent are mixed and melt-kneaded at a temperature equal to or higher than the softening temperature of the coating agent by a kneading machine such as a Banbury mixer, an extruder, a kneader, or a three-roll mill. , To obtain a mixture. As another method, dissolve the resin in the solvent of the coating agent and add a light-to-heat conversion agent, ball mill, attritor, sand mill, Banbury mixer, extruder, kneader,
The mixture is dispersed and kneaded by a disperser and a kneader such as a three-roll mill, and the kneaded product is dried or added to a non-solvent to precipitate to obtain a mixture. Among these methods, the melt-kneading method is preferable because the adhesion between the light-to-heat conversion agent and the coating agent is better and the subsequent dispersing process and desorption over time are less than the other methods. Next, the thus obtained mixture is dry-pulverized, and then wet-dispersed with a dispersing agent such as a ball mill, an attritor, a paint shaker, and a sand mill to obtain a concentrated toner liquid. The toner concentrate is added to a carrier liquid containing a charge control agent to obtain a polymer fine particle dispersion.

Others (concentration, ratio, etc.) The particle concentration (concentration of the coating resin and the photothermal conversion agent) is not particularly limited, but is about 0.1 g to 10 g per liter when using a working solution. In case, the concentration is about 10 g to 500 g. The usage ratio of the coating resin and the light-to-heat conversion agent is such that the coating resin is about 0.1 to 20 parts by weight per 1 part by weight of the light-to-heat conversion agent.
It is preferred to use parts by weight, especially about 0.5 to 5 parts by weight. The dispersant is used in an amount of about 0.1 to 10 parts by weight, preferably about 0.2 to 5 parts by weight, based on 1 part by weight of the photothermal conversion agent. The charge control agent is about 1 × 10 ^-4 to 1 mol / l, preferably about 1 × 1 in the case of a toner concentrate.
0 ^-3 to 1 × 10 ^-1 mol / liter is used. In the case of a diluting solution, about 1 × 10 ⁻⁶ to 1 × 10 ⁻² mol / l, preferably about 1 × 10 ⁻⁵ to 1 × 10 ⁻³ mol / l is used.

As the electrically insulating liquid used in the present invention, various kinds of known liquids can be used.
It is desirable to select a non-aqueous solution having a resistivity of ⁹ Ω · cm or more and a dielectric constant of 3 or less. In addition, it is necessary to select one having low solubility in the coating agent. Generally, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, polysiloxanes, and the like can be used, but isoparaffins are preferred in terms of volatility, stability, toxicity, odor, and the like. Based petroleum solvents are preferred. Examples of the isoparaffin-based petroleum solvent include Isopar G, Isopar H, Isopar L, Isopar K manufactured by Esso, and Shell Sol 71 manufactured by Shell Petroleum Company.

The polymer fine particles used in the present invention can be subjected to a heat treatment for the purpose of improving the stability with time and sedimentation of the particles. As the heating conditions, it is preferable to perform the heat treatment at a temperature in a range from a temperature 20 ° C. lower than the softening start point of the polymer resin used for the particles to a softening temperature.

Next, the printing section of the planographic printing press of the present invention will be described with reference to FIGS. FIG. 1 is a schematic view of an example of an apparatus for forming an image forming layer and directly performing image forming and plate making on the printing press of the present invention. The sheet or web-shaped printing paper (substrate to be printed) 12 is sandwiched between the impression cylinder 7 and the blanket cylinder 6. The blanket cylinder 6 is in contact with the cylindrical plate cylinder 1, and is a transfer unit for transferring an inked image described later from the cylindrical plate cylinder 1 to the printing material 12.
This cylindrical plate cylinder 1 is provided with a hydrophilic support 11 on the outer peripheral surface. The hydrophilic support 11 can be made of paper, plastic film or metal whose surface has been hydrophilized. A particle layer (image forming layer) 13 formed by electrodeposition of a charged dispersion (also referred to as toner) formed on the outer peripheral surface of the hydrophilic support 11 is attached to the cylindrical plate cylinder 1 and described later. Is formed by the electrodeposition apparatus 2.

After the image forming layer 13 is formed, an image is formed on the hydrophilic support 11 in accordance with digital data to be printed by a drawing device (imaging unit) 3 provided in proximity to the cylindrical plate cylinder 1. An infrared laser is scanned and exposed on the surface of the formation layer 13 to print an image with accurate registration. On the surface of the image forming layer 13, an image pattern composed of an ink receiving area (a heat-sealed portion of polymer particles, hydrophobic) and an ink repelling area (a non-heat-sealed portion of polymer particles, hydrophilic) is formed. Form.

During image formation (image formation), the printing press is in a “printing operation off” mode (an operation mode in which no printing operation is performed). That is, in the "printing operation off" mode, the cylindrical plate cylinder 1 is not in contact with any other cylinder. When the image forming by the drawing device 3 is completed, the printing press is switched to a “printing operation on” mode (an operation mode of performing a printing operation), and the ink / water supply device 4 provided near the cylindrical plate cylinder 1 causes The surface of the imaged image forming layer 13 on the support 11 is inked in a conventional or anhydrous offset manner. The non-image portion of the unexposed portion has good removability (developability) because the fine particles are in a certain amount at the initial stage of printing, and the fountain solution on a printing machine is used.
Or it can be removed by ink.

A plate surface cleaning device (cleaning unit) 5 is mounted near the cylindrical plate cylinder 1. The plate surface cleaning device 5 wipes off the ink, water and most of the imaged image forming layer 13 on the hydrophilic support 11 of the cylindrical plate cylinder 1 used in the previous printing operation, and then removes the chemical. The toner image portion adhered and fixed to the plate surface by processing and / or physical processing is removed. Here, the chemical treatment is a chemical substance or a solution thereof that swells and / or dissolves the toner resin described above (hereinafter, referred to as a chemical treatment liquid), and applies the chemical treatment liquid to a printing plate having a toner image portion. Alternatively, the same plate surface is immersed in a chemical treatment solution. In addition, the physical process refers to a process of physically exposing a new surface by, for example, scraping off a toner image portion on a plate surface. The plate cleaning device 5 is similar to the well-known "blanket washer" used in modern printing presses to clean blanket cylinders between one printing operation and the next, but with a cylindrical plate cylinder. 1 in that the following chemical treatments may have to be added to dissolve most of the imaged layer 13 formed above.

Examples of the above-mentioned chemical treatment liquid include ethers such as tetrahydrofuran and triethylene glycol dimethyl ether, aromatic organic solvents such as toluene, paraffin hydrocarbons, ketones such as methyl ethyl ketone, dimethyl sulfoxide, dimethylformamide and the like. These may be used in combination, or of course, they may be used as a solution diluted with a diluting solvent. Chemical treatment agents include sulfates, phosphates, polyphosphates, silicates,
An aqueous solution containing salts such as organic phosphonic acid and oxalate, a surfactant, a water-soluble polymer compound, a wetting agent, an organic solvent having an ink dissolving action, and the like can be used. In addition, any of acidic and alkaline pH can be used.

FIG. 2 shows a cylinder 1 on a printing press according to the invention.
1 is a schematic view of an on-board electrodeposition apparatus 2 provided in the apparatus. The electrodeposition apparatus 2 includes a hydrophilic support 11 and an opposing electrode (also referred to as an electrodeposition head) 2 installed on the outer peripheral surface of the cylindrical plate cylinder 1 as described above.
When the plate cylinder 1 is rotated by applying an electric field (DC power supply 27) while supplying the electrodeposition liquid (also referred to as a charged dispersion or toner) from the electrodeposition liquid supply liquid slit 21 to between 0 and 0, the plate cylinder 1 is supported. This is an apparatus for continuously electrodepositing the dispersion on a body 11 to form a particle layer (image forming layer) 13. Electrodeposition equipment 2
As shown in FIG. 2, the electrodeposition liquid tank 25, the pump 26,
Electrodeposition head 20, blade (or roller) 24, electrodeposition liquid supply liquid slit 21, electrodeposition liquid recovery first slit 22
And a second slit 23 for recovering the electrodeposition liquid, and has a configuration such that a DC voltage can be applied between the electrodeposition head 20 and the hydrophilic support 11 provided on the plate cylinder 1. The distance between the hydrophilic support 11 and the electrodeposition head 20 is 1 mm to 20 m
m is preferred. The applied voltage is preferably 100 V to 5000 V, and the amount of electrodeposition is preferably 0.1 to 2 g. The electrodeposition head 20 may be directly installed on the printing press or may have a structure independent of the printing press, and may be installed on the printing press at the time of use. After the electrodeposition, the carrier liquid of the fine particles is removed. As a method for removing the carrier liquid, there are methods such as an air knife squeeze, a corona squeeze, and a roller squeeze, which are collected by the first electrodeposition liquid recovery slit 22 and the second electrodeposition liquid recovery slit 23.

[Support] As the support for forming the hydrophilic layer containing the anatase-type titanium oxide fine particles,
Paper, synthetic paper, paper laminated with synthetic resin (eg, polyethylene, polypropylene, polystyrene), plastic film (eg, polyethylene terephthalate, polycarbonate, polyimide, nylon, cellulose triacetate), metal plate (eg, aluminum, aluminum alloy, lead) , Iron, copper), and paper or plastic film on which these metals are laminated or deposited. Aluminum plates, plastic films, paper and synthetic paper are preferred. Further, a composite sheet in which an aluminum sheet is laminated on a polyethylene terephthalate film is also preferable. Aluminum plates and plastic films are more preferred, and aluminum plates are particularly preferred. When a hydrophobic material such as a plastic film is used, it can be used as a hydrophilic support by providing a hydrophilic undercoat layer (described later).

The case where an aluminum plate is used as a support will be further described. The aluminum support is subjected to a surface treatment such as a surface roughening treatment (graining treatment) or a surface hydrophilic treatment as necessary. The surface roughening treatment may be performed by an electrochemical graining method (eg, a method of graining an aluminum plate by passing an electric current in a hydrochloric acid or a nitric acid electrolyte) and / or a mechanical graining method (eg, an aluminum plate surface). By a wire brush graining method using a metal wire, a ball graining method for graining the aluminum surface with a polishing ball and an abrasive, and a brush graining method for graining the surface with a nylon brush and an abrasive).

Next, the grained aluminum plate is chemically etched with an acid or an alkali. An industrially advantageous method is etching using an alkali. Examples of the alkaline agent include sodium carbonate, sodium aluminate, sodium metasilicate, sodium phosphate, sodium hydroxide, potassium hydroxide and lithium hydroxide. The temperature of the alkaline solution is preferably in the range of 1 to 50% by weight. The temperature of the alkali treatment is preferably in the range of 20 to 100 ° C. Further, it is preferable to adjust the processing conditions so that the amount of aluminum dissolved is 5 to 20 g / m ² .

Usually, after the alkali etching, the aluminum plate is washed with an acid to remove dirt (smut) remaining on the surface. Preferred acids are nitric, sulfuric, phosphoric, chromic, hydrofluoric and borofluoric acids. The smut removal treatment after the electrochemical graining treatment can be performed by a known method such as a method of contacting with sulfuric acid at a concentration of 15 to 65% by weight at 50 to 90 ° C.

The aluminum plate having been subjected to the surface roughening treatment as described above can be subjected to an anodic oxidation treatment or a chemical conversion treatment as required. The anodic oxidation treatment can be performed by a known method. Specifically, in an acid solution,
An anodic oxide film is formed on the aluminum surface by passing a direct current or an alternating current through the aluminum plate. Examples of acids include sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid and benzenesulfonic acid. Anodizing conditions vary depending on the electrolyte used. Generally, the concentration of the electrolyte is 1 to 80% by weight, the temperature of the electrolyte is 5 to 70 ° C., the current density is 0.5 to 60 amps / dm ² , the voltage is 1 to 100 V, and the electrolysis time is 10 to 10%. It is preferably within a range from 100 to 100 seconds.

Particularly preferred anodic oxidation methods are a method of anodic oxidation in sulfuric acid at a high current density and a method of anodic oxidation using phosphoric acid as an electrolytic bath. After the anodizing treatment, the aluminum plate may be subjected to an alkali metal silicate treatment (for example, a treatment of immersing the aluminum plate in an aqueous solution of sodium silicate). In order to improve the adhesion between the aluminum support and the curable layer and the printing characteristics, an undercoat layer may be provided on the support surface.

[Undercoat Layer] The undercoat layer is provided as a hydrophilic layer not only on the aluminum support described above, but also on a support (eg, a plastic film) whose surface is not sufficiently hydrophilic. Components constituting the undercoat layer include polymers (eg, gelatin, casein, polyvinyl alcohol, ethyl cellulose, phenolic resin, styrene-maleic anhydride resin, polyacrylic acid); amines (eg, monoethanolamine, diethanolamine, triethanolamine) , Tripropanolamine) and their hydrochlorides, oxalates or phosphates; monoaminomonocarboxylic acids (eg, aminoacetic acid, alanine); oxyamino acids (eg, serine, threonine, dihydroxyethylglycine); sulfur-containing amino acids (Eg, cysteine, cystine); monoaminodicarboxylic acid (eg, aspartic acid, glutamic acid); diaminomonocarboxylic acid (eg, lysine); amino acid having an aromatic nucleus (eg, p-hydroxyphenylglycine, phenylalanine, ant) Sulfonyl); aliphatic amino acid (e.g., sulfamic acid, cyclohexylsulfamic acid); and (poly) aminopolyacetic acid (e.g.,
Ethylenediaminetetraacetic acid, nitrilotriacetic acid, iminodiacetic acid, hydroxyethyliminodiacetic acid, hydroxyethylethylenediamineacetic acid, ethylenediaminediacetic acid, cycloethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and glycol etherdiaminetetraacetic acid). A compound in which some or all of the acid groups of the above compounds have become salts (eg, sodium salt, potassium salt, ammonium salt) can also be used. The above components can be used in combination of two or more. When a plastic film is used as the support, hydrophilic fine particles (eg, silica powder) are preferably added to the hydrophilic undercoat layer instead of the graining treatment of the aluminum support.

[Drawing Method] Next, an image forming and drawing method in this printing method will be described. By a drawing device (imaging unit) 3 mounted near the cylindrical plate cylinder 1,
The hydrophilic support 1 according to digital data to be printed
The surface of the upper image forming layer 13 is scanned and exposed with an infrared laser to form an image portion with accurate registration. The imagewise exposure of the image forming layer 13 can be used as long as the light source emits active light. A preferable light source is a light source that emits light in a long wavelength region to an infrared region of visible light. As a laser light source, image exposure is performed using a solid-state laser, a semiconductor laser, and a YAG laser that emit infrared light having a wavelength of 760 nm to 1200 nm. In addition, excimer laser (XeF),
He-Cd laser, N ₂ laser, LD pumped Nd; Y
The second obtained by the AG laser internal cavity type SHG
External resonator type using BBO crystal for harmonics
-HG, Q switch operation LD pumped solid-state laser can also be used. Preferred light sources other than laser light include xenon discharge lamps, mercury lamps, tungsten lamps,
A tungsten-halogen lamp, a xenon arc lamp, a fluorescent lamp, or the like can be used, and a light source containing infrared rays is particularly preferable.

The writing of an image may be performed by either a surface exposure method or a scanning method. When a surface exposure light source is used, the preferable exposure amount changes depending on the illuminance, but usually, the surface exposure intensity before modulation with a print image is 0.1 to 1.
0 J / cm ² , preferably 0.1 to 1
More preferably, it is in the range of J / cm ² . If the support is transparent, it can be exposed through the support from the back side of the support. The exposure time can be selected in a wide range as long as a necessary exposure amount is provided. Usually 0.0
1 msec to 10 minutes, preferably 0.01 msec to 1
It is preferable to select the exposure illuminance so that the above-described exposure intensity can be obtained by irradiation with light for one minute.

[0069]

[Example 1]

(Production of aluminum support) JI having a thickness of 0.24 mm
The surface of the aluminum plate according to SA-1050 was grained with a nylon brush and an aqueous suspension of pamistone (400 mesh), and then thoroughly washed with water. Next, the film was immersed in a 10% by weight aqueous solution of sodium hydroxide at 70 ° C. for 60 seconds for etching, and then washed with running water. 20% by weight
And then washed with water. The obtained aluminum plate was subjected to a square wave alternating current (condition:
The voltage at the time of the anode is 12.7 V, the ratio of the amount of electricity at the cathode to the amount of electricity at the anode is 0.9, and the amount of electricity at the anode is 160 coulomb / dm.
² ) Using ¹ ) containing 0.5% by weight of aluminum nitrate
Electrolytic surface-roughening treatment was performed in a weight% nitric acid aqueous solution. The surface roughness of the obtained plate was 0.6 μm (Ra indication).
Subsequent to this treatment, the substrate was immersed in a 1% by weight aqueous solution of sodium hydroxide at 40 ° C. for 30 seconds, and then treated in a 30% by weight aqueous solution of sulfuric acid at 55 ° C. for 1 minute. Next, the thickness is 2.5g
/ Dm ² to become so under the conditions of a current density of 2A / dm ² using a direct current in 20 wt% aqueous solution of sulfuric acid was anodized. This was washed with water and dried to prepare a support.

The support thus prepared was prepared by using No. 3 sodium silicate (S
IO _2: 28 to 30 wt%, Na ₂ O: 9 to 10 wt%,
Fe: 0.02% by weight or less 2.5% by weight aqueous solution (p
H: 11.2) at 70 ° C. for 13 seconds and washed with water.
The amount of silicate measured by X-ray fluorescence analysis was 10 mg / m
^{Was 2} .

(Formation of Photocatalytic Titanium Oxide Hydrophilic Layer) The following compositions were mixed to obtain a photocatalytic titanium oxide dispersion.

[Composition of Dispersion of Photocatalyst Titanium Oxide] Photocatalyst Titanium Oxide Sol (30% solution) Titanium Oxide Slurry STS-02 (Ishihara Sangyo Co., Ltd.) 167 g Tetramethoxysilane 25 g Trimethoxysilane 25 g Distilled water 830 g ・ 700 g of ethanol

The dispersion was coated on the aluminum substrate using a wire bar and dried at 110 ° C. for 20 minutes to form a hydrophilic layer having a coating amount of 2 g / m ² . 4 more
00W high-pressure mercury lamp (UVL-4 manufactured by Riko Kagaku Sangyo Co., Ltd.)
00P), the hydrophilic layer was illuminated for 10 minutes at a distance of 10 cm from the mercury lamp.

(Preparation of High Polymer Particles) 1 part by weight of carbon black (Mitsubishi Chemical # 40) and 2 parts by weight of a synthetic product of stearyl methacrylate / methyl methacrylate (molar ratio 1: 9) were mixed. And melt-kneaded at 120 ° C. for 30 minutes using a three-roll mill. After cooling to room temperature,
It was coarsely and finely ground by a hammer mill and a pin mill. The pulverized product was dispersed in the following composition.

(Composition at the time of polymer particle dispersion) 3 parts by weight of the above pulverized product 20 parts by weight of a 5% by weight solution of Soprene 1205 (manufactured by Asahi Kasei Corporation)

For dispersion, preliminary dispersion was first performed with an attritor, and then main dispersion was performed with a super mill at a peripheral speed of 10 m / sec for 2 hours. The solid content concentration of the dispersion thus obtained is 13% by weight. The temperature during dispersion was 35 ° C.

The following operations were carried out on the dispersion thus obtained.
Made a work. The above dispersion is diluted twice with Isopar G
And in the general formula (1) described in the present specification.
R₁: NC₈H₁₇, R_Two: NC₁₃H₂₇CO, X: N
i, A: C_TwoH _Four, A charge control agent represented by n = 2
1 × 10 per g of particles^-FourMolar content, 50 ° C-3 days
Heat treatment was performed for a while. During that time, do not perform any stirring operation
Was. The amount of charge is measured with the device described in JP-A-57-58176.
The result was 35 mV / cm. Also, the particle size
Measured by HORIBA, Ltd. CAPA500
The result was 0.46 μm. Further, the resulting dispersion
The solution is diluted with Isopar G to give a solid content of 0.1 g.
/ Liter.

Next, the aluminum support substrate on which the photocatalytic titanium oxide hydrophilic layer was formed was immersed in the polymer fine particle dispersion, and the aluminum support substrate was used as a positive electrode. A negative counter electrode was placed in the dispersion at a distance of 1 cm. Then, a DC voltage of 2000 V was applied between the positive electrode and the negative electrode, and an electrodeposit of high molecular weight polymer particles of 1.0 g / m ² was formed on the substrate. The wavelength is 83
Exposure was performed with a semiconductor laser emitting 0 nm infrared light. After the exposure, without development, the printing machine (RYOBI3200C
CD) as usual. As a result, in the first 50 sheets,
The unexposed portion was completely removed, and a stain-free printed matter was obtained, so that printing of 10,000 sheets was possible.

After the printing was completed, the ink remaining on the plate surface and the image area were removed using a cloth impregnated with an ultraplate cleaner (manufactured by ABCChemica 1. Co. Ltd., UK), and a 400 W high-pressure mercury lamp (Science and Technology) UV manufactured by Sangyo Co., Ltd.
L-400P), and irradiating with light for 10 minutes at a distance of 10 cm from the mercury lamp to regenerate the hydrophilic support. When high molecular weight polymer particles were electrodeposited and exposed to laser light, printing was performed. As a result, a good printed matter having a sufficient density in the image area and no stain on the unexposed area was obtained.

Comparative Example 1 Example 1 was repeated except that an aluminum substrate without a photocatalytic titanium oxide layer was used as the hydrophilic layer.
In the same manner as described above, high-molecular polymer fine particles were electrodeposited, laser-exposed, and printed. In the first printing process, a good printed matter having a sufficient density in the image area and no stain on the unexposed area was obtained, but after washing the plate in the same manner as in Example 1, the high molecular polymer fine particles were again obtained. Was subjected to electrodeposition and laser exposure for printing, and the obtained printed matter was noticeably stained in a non-image area.

Example 2 The aluminum support substrate having the photocatalytic titanium oxide layer prepared in Example 1 was set on a plate cylinder of an offset printing machine manufactured by Tokyo Aviation Instruments Co., Ltd. Further, as shown in FIG. 2, the electrodeposition unit was placed at a distance of 5 mm from the aluminum substrate. The aluminum support was used as a positive electrode, and a DC voltage of 2000 V was applied between the aluminum support and the electrodeposition unit. Next, the polymer particle dispersion prepared in Example 1 was put into an electrodeposition tank, and was sent between the electrodeposition unit and the aluminum support by a pump.
The aluminum support is a positive electrode, the electrodeposition unit is a negative electrode, and the distance between the positive and negative electrodes is 2 m.
m, and a DC voltage of 2000 V was applied between both electrodes to form an electrodeposit of 0.6 g / m ² of polymer fine particles on the substrate. This was exposed to a semiconductor laser emitting infrared light having a wavelength of 830 nm. After exposure, without development, IF201 as a fountain solution (Fuji Photo Film Co., Ltd.)
As GEOS ink (Dainippon Ink Co., Ltd.)
Was used for printing. As a result, a printed matter free of background stain was obtained from the 30th sheet, and 10,000 sheets could be printed.

Example 3 In an arrangement as shown in FIG. 1, an ultraplate cleaner (ABC Chemical Co. Ltd., UK) was used.
Plate cleaning device 5 equipped with a rag impregnated with) is removed, the ink and image portions remaining on the plate after printing in Example 2 are removed and dried, and ultraviolet irradiation is performed by an ultraviolet irradiation device 8 to perform hydrophilic support. Regenerated body. Next, in the same manner as in Example 2, high-molecular polymer fine particles were electrodeposited and laser-exposed, and printing was performed. As a result, a good printed matter having a sufficient density in the image area and no stain on the unexposed area was obtained. Obtained.

[0083]

As described above, the lithographic printing plate precursor according to the present invention has a hydrophilic layer containing anatase type titanium oxide fine particles and a resin having a siloxane bond represented by the above general formula (I). By forming a heat-sealed image of the electrodeposited fine particles and removing the non-image area on a printing machine, printing can be performed without performing a developing operation, and clear image quality without background contamination Can be used as a lithographic printing plate capable of printing a large number of prints. The present invention utilizes a resin having a siloxane bond as a resin for dispersing anatase-type titanium oxide, and particularly, by forming a film using a sol-gel method, the strength of the film as a hydrophilic layer, and oxidation. There is an advantage that the titanium particles are excellent in uniform dispersibility. Furthermore, the lithographic printing plate precursor of the present invention can regenerate the non-image area to its original hydrophilic state by removing the printing ink of the used lithographic printing plate and irradiating it with ultraviolet light, and even after repeated use, the stain can be removed. No good printed matter is obtained. The lithographic printing plate precursor, the printing method and the printing press of the present invention are capable of eliminating the process of plate making by performing electrodeposition and image exposure of an image forming layer on a printing press.
To Cylinder (CTC) printing method can be realized. Normal P
Eliminates the time and cost required to make the S plate,
This makes it possible to create printed materials with low cost and short delivery time. Further, plate exchange work after printing is not required, plate waste is not generated, and time, labor and cost can be reduced.

[Brief description of the drawings]

FIG. 1 is a schematic view of an example of a printing press according to the present invention.

FIG. 2 is a schematic view of an on-press electrodeposition apparatus provided in the printing press of FIG.

[Explanation of symbols]

 1: Plate cylinder 2: Electrodeposition device 3: Drawing device 4: Ink / water supply device 5: Print cleaning device 6: Blanket cylinder 7: Impression cylinder 8: Ultraviolet irradiation device 11: Hydrophilic support 12: Printed material 13: Image forming layer 20: electrodeposition head 21: electrodeposition liquid supply slit 22: electrodeposition liquid recovery first slit 23: electrodeposition liquid recovery second slit 24: blade 25: electrodeposition tank 26: pump 27: DC power supply

Continued on the front page F term (reference) 2H025 AA00 AA01 AA12 AB03 AC08 AD01 AD03 CB14 CC20 DA18 DA36 EA03 FA03 FA48 2H096 AA00 AA07 BA20 CA05 CA11 EA04 JA04 LA02 LA30 2H114 AA04 AA23 BA01 DA03 DA04 DA08 DA25 DA78 DA53 DA73 DA53 DA73 DA73 DA73 DA73 DA53 DA73 DA73 DA73 DA73 DA03 DA73 DA03 DA03 DA03 DA03 DA03 DA03 DA03 DA03 DA05 GA03 GA05 GA06 GA08 GA09 GA29 GA34 GA38

Claims (4)

[Claims] An electric field is applied between a charged high molecular polymer fine particle dispersion and a hydrophilic support having a hydrophilic layer containing anatase type titanium oxide fine particles, and an electric field is applied to the support. An original plate for a lithographic printing plate, comprising an image forming layer containing the adhered high molecular weight polymer particles. 2. A dispersion comprising a hydrophilic support having a hydrophilic layer containing fine particles of anatase type titanium oxide provided on a plate cylinder of a printing press, and a high molecular polymer particle having a charge in an electrically insulating liquid. Applying an electric field between the liquid and the liquid, electrodepositing the polymer particles on the support to form an image-forming layer, exposing the image-forming layer to an image, ink, water or rubbing. A printing method comprising a step of performing printing after removing a non-image portion. 3. After being subjected to printing by the printing method,
The image portion on the surface of the printing plate is subjected to plate cleaning by chemical or physical treatment to remove the image of the plate, and further comprises a step of regenerating the hydrophilic support by irradiating ultraviolet rays. The printing method according to claim 2, wherein 4. A plate cylinder on which a hydrophilic support having a hydrophilic layer containing anatase-type titanium oxide fine particles is installed, and an electric field is applied between the support and the charged high-molecular polymer fine particles to apply the electric field. A printing machine comprising: a device for electrodepositing the high-molecular polymer fine particles on a support to form a particle layer; a drawing device having an exposure light source; a plate surface cleaning device; and an ultraviolet irradiation device.