JP2002127354A - Method and apparatus for offset printing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for offset printing with which an original printing plate is easily made up without use of an alkaline developing solution and with a print quality improved at a practical level in distinguishability between an image part and a non-image part of a printed face, and can be repeatedly used. SOLUTION: In this method and an apparatus for offset printing, the original printing plate is made hydrophilic when heated at a temperature required for developing high temperature hydrophilicity. Then, on a surface of the plate a hydrophobic image area is formed by imagewise coating with an ink-jet method a solution including at least one of chemical compounds expressed by GnJM4-n (G is a hydrophobic organic group; J is an element with an atomic value of 4 selected out of C, Si, Ge, Ti, Zr, and Sn; M is halogen or an alkoxy group; and (n) is an integer of 1 to 3). A method and an apparatus for reusing the original printing plate after the surface of the plate used is cleaned so that the remaining ink is removed, then the chemical compound is thermally decomposed, are also provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to the field of general light printing,
In particular, the present invention relates to offset printing, and more particularly to a novel offset printing method and a printing original plate capable of easily producing a printing plate. Among them, the offset printing method, in which the plate making is particularly simple, and enables the repeated use of the printing original plate,
The present invention relates to an original plate for printing and a printing apparatus using the same.

[0002]

2. Description of the Related Art The offset printing method has been widely used particularly because of a simple printing plate manufacturing process among many printing methods, and is the main printing method at present. This printing technique is based on the immiscibility of oil and water, with the image areas selectively retaining oily material or ink and the non-image areas selectively retaining fountain solution. Therefore, when the surface to be printed is brought into direct contact with the surface to be printed or indirectly through an intermediate called a blanket, the ink in the image area is transferred and printing is performed.

The main method of offset printing is a PS plate having an aluminum substrate as a support and a diazo photosensitive layer coated thereon. In the PS plate, the surface of the aluminum substrate, which is the support, is subjected to graining, anodic oxidation, and other treatments to enhance the ink receiving capacity of the image area and the ink repulsion of the non-image area, thereby improving the printing durability. It is the most common and main printing method in the general printing field, because it has characteristics such as printing durability and high definition of the printing surface in addition to simplicity, such as improvement of the printing surface. With the spread of the offset printing method, further simplification has been demanded, and many simple printing methods have been proposed.

Representative examples include the Copyrapid offset printing plate commercially available from Agfa-Gevaert, and US Pat.
No. 11656, Japanese Patent Application Laid-Open No. 7-56351, and the like. This is a printing method based on the production of a printing plate by a silver salt diffusion transfer method. Since the image is lipophilic and can be directly used as a printing plate, it is practically used as a simple printing method. However, although simple, this method also requires a diffusion transfer development step using an alkaline developer. There is a demand for a simple printing method that does not require a developing step with a developer.

As a method for meeting the demand, with the recent development of office equipment and the development of OA, various dry-type lithographic printing plates such as electrophotographic printers, thermal transfer printers, and ink jet printers are also used in the printing field. There has been proposed an offset lithographic printing method in which a printing plate is directly formed without performing a complicated process such as wet development using an image recording method. Among the methods proposed, a method using recording by an ink jet printer is considered to have high applicability to simple plate making because ink jet recording is a recording method capable of high-speed printing with low noise.

As an ink jet recording system, a so-called electric field control system in which ink is ejected by using an electrostatic attraction force, and a so-called drop-on-demand system in which ink is ejected by using a vibration pressure of a piezo element (pressure). Various types of recording methods, such as a so-called bubble (thermal) jet method, in which ink is ejected by using pressure generated by forming and growing bubbles by high heat, and a so-called bubble (thermal) method, have been proposed. Thus, a highly accurate image can be obtained.

On these conventional direct drawing type lithographic printing original plates,
As an inkjet ink used for forming an image by an inkjet recording method, an aqueous ink using water as a main solvent and an oil-based ink using an organic solvent as a main solvent are generally used. However, the water-based ink has a problem that an image on a plate material bleeds and a drawing speed is reduced due to slow drying. In order to alleviate such a problem, a method using oil-based ink using a dispersion medium as a non-aqueous solvent is disclosed in Japanese Patent Application Laid-Open No. Sho 54-117203.
Issue.

However, even when oil-based ink is used, blurring is observed in an actually made image, and further blurring occurs when printing is performed. Further, the number of printed sheets is limited to several hundred at most, and is insufficient. Met. In addition, such an ink has a problem that clogging is likely to occur in a nozzle that discharges a minute ink droplet that enables a high-resolution plate-making image. Further, the electrostatic discharge type ink jet system has a problem that the charging of the oil droplets causes distortion of the image and deteriorates the image quality.

The application of ink jet type image recording to plate making involves the above-mentioned defects even when oil-soluble ink is used.
A further fundamental problem is that the original printing plate is designed to maximize the printing performance, and therefore, the adhesion between the image material and the surface layer of the original plate is insufficient for recording an ink-jet image. The strength of the part is weak, and the printing durability tends to be insufficient.

As an attempt to prevent clogging of nozzles by oil-based ink for a general inkjet printer, for example, a method of improving the dispersion stability of pigment particles (JP-A-4-25573 and JP-A-5-25413). And a method of including a specific compound as an ink composition (Japanese Patent Application Laid-Open No. 3-796).
No. 77, No. 3-64377, No. 4-2023
No. 86, No. 7-109431, etc.). However, when any of these is used for image formation on a lithographic printing plate, none of them can solve the problem of insufficient image strength at the time of printing and cannot satisfy the printing durability.

The method of forming an image on an original plate having an image receiving layer containing zinc oxide by an ink jet method and then desensitizing the non-image portion by desensitizing the non-image portion to perform printing is performed by using the following method. -The image quality of printed matter is good, and it is possible to print many sheets. However, the complexity of wet processing such as the use of a desensitizing solution in preparing a printing plate and the necessity of a liquid containing a desensitizing component similar to the desensitizing solution as a fountain solution during printing is essential. Is mentioned. In addition, since a fountain solution containing the above components is used, depending on the printing ink to be used, it may interact with the components in the printing ink and cause stains on a printed material. There is a problem that the used color printing cannot be performed.

As described above, the adoption of the ink jet type drawing means in the stencil for light printing of a lithographic plate is extremely promising in terms of simplification of the stencil making operation. The above-mentioned weak points are obstacles to practical use, for example, the adhesive strength is low, the printing durability is poor, the ink is clogged, and the image is distorted by the influence of static electricity.

[0013]

SUMMARY OF THE INVENTION In view of the above circumstances, it is an object of the present invention to eliminate the need for an alkaline developer, to make a plate easily, and to discriminate an image area and a non-image area on a printing surface. It is an object of the present invention to provide an offset printing method which has a printing quality of a practical level in which the printing quality is improved, and which can use a printing plate repeatedly. A second object of the present invention is to provide a printing apparatus capable of performing printing at a practical level of print quality by a simple operation using the above-described printing method and repeatedly using a printing original plate.

[0014]

Means for Solving the Problems In order to achieve the above object, the present inventors have made intensive studies on the possibility of an ink jet system having an advantage in simplicity of plate making. When a search was made for a means for improving the adhesiveness between the substrate and an image-bearing original plate (such as the surface of a support), a compound satisfying both the ink receptivity and the adhesiveness to the substrate described below was found. By applying the method to the plate making of the system, it is possible to secure the printing durability, to improve the discrimination of the image part / non-image part, and to suppress the printing smear. The object of the present invention has been achieved in combination with simplicity. That is, the present invention is shown by the following items.

1. A hydrophobic image area is formed by image-wise drawing a solution containing at least a compound represented by the following general formula (1) as an ink on an ink-jet method on the surface of an offset printing plate having a hydrophilic surface, An offset printing method, wherein the printing is performed by contacting the image area with a printing ink to form a printing surface in which the area has received the ink. G _n JM _4-n (1) In the general formula (1), G represents a hydrophobic organic group,
J represents an element having a valence of 4 selected from C, Si, Ge, Ti, Zr and Sn, M represents a halogen or an alkoxy group, and n represents an integer of 1 to 3.

2. 2. The offset printing method as described in 1 above, wherein the offset printing plate having a hydrophilic surface is a printing plate having photocatalytic activity, the surface of which is made hydrophilic by irradiating the plate with actinic light.

3. After removing the ink remaining on the plate surface of the printing plate used for printing by washing and subjecting the plate to a heat treatment at a temperature not lower than the thermal decomposition temperature of the compound represented by the general formula (1), the printing plate is used as a printing plate. 3. The printing method according to the above 1 or 2, wherein printing is performed by repeating the operation described in the above 1 or 2.

4. The surface of the printing plate is made of TiO ₂ , RT
iO ₃ (R is an alkaline earth metal atom), AB _2-x C _{x
D 3-x E x O 10} (A is a hydrogen atom or an alkali metal atom, B is an alkaline earth metal atom or a lead atom, C is a rare earth atom, D is a metal atom belonging to Group 5A elements of the periodic table, E
Is a metal atom belonging to the 4A group element, and x represents an arbitrary numerical value of 0 to 2), SnO ₂ , Bi ₂ O ₃ , ZnO, Z
and rO, characterized in that it is constituted by at least one metal oxide selected from the GeO ₂ and FeO _{y (y} = 1.0~1.5) according to any one of the above 1 to 3 Offset printing method.

5. An offset printing apparatus used in the method according to any one of the above items 1 to 4, wherein an original plate mounting portion on which a printing original plate having photocatalytic ability is mounted, and the surface of the original plate irradiated with active light. Irradiating means for making hydrophilic, drawing means for forming a hydrophobic image area by applying ink jet drawing on the original plate, and supplying printing ink to the image area so that the printing area on which the image area has received the ink is printed. An offset printing apparatus comprising: an ink supply unit to be formed; and a printing unit that performs printing by bringing the printing surface into contact with a surface to be printed.

6. The method according to the above item 5, further comprising an ink washing means for removing ink remaining on the printing plate after printing, and a heating means for heating the washed printing plate surface to a temperature equal to or higher than the thermal decomposition temperature of the compound of the general formula (1). Offset printing equipment.

7. 7. The offset printing apparatus according to the above item 5 or 6, wherein at least the exposure unit, the drawing unit, the ink supply unit and the ink removal unit are arranged around the plate cylinder.

8. The printing plate constitutes a part of the plate cylinder, and at least an exposure unit, a drawing unit, an ink supply unit,
The offset printing apparatus according to any one of claims 5 to 7, wherein an ink removing unit and a plate surface heating unit are disposed around the plate cylinder.

The offset printing method of the present invention is based on forming an image area by drawing a compound of the formula (1) on a hydrophilic image-carrying surface (surface for a printing original plate) using an ink jet apparatus. . The compound of the general formula (1) forms an image-like hydrophobic surface and accepts a printing ink,
At the same time, the adhesive strength to the image carrying surface (the surface of the original printing plate) is strong, so that the mechanical strength of the image area can be maintained, the printing durability is secured, and the hydrophilicity of the image carrying surface can be enhanced, so that the discrimination effect can be obtained. It is possible to form a printing surface which is high and has less stain. In the present invention, the hydrophilicity of the offset printing plate having a hydrophilic surface does not need to be hydrophilic before drawing by the ink jet method, and is not required to be hydrophilic after finishing drawing and before starting printing. Processing, for example, when irradiating with active light again is included.

As the image bearing surface, any material can be used as long as it is a hydrophilic surface. In a preferred embodiment, a solid surface having photocatalytic activity, for example, titanium oxide can be used. In the present invention, "a substance having photocatalytic ability" refers to, for example, titanium oxide,
A substance that changes its optical properties such that when the surface of the substance is irradiated with light of a specific wavelength, the surface changes to a hydrophilic property.
Further, light of a specific wavelength that causes such a change in optical properties is called “active light”.

Another advantage of the offset printing method of the present invention is that, despite the strong adhesion of the compound of the general formula (1) to the image bearing surface, the compound is thermally decomposed by heating to remove hydrophobic groups. Has the property that it is detached and the surface hydrophobic region disappears. Therefore, after printing is completed, an appropriate solvent is selected to remove the ink adhering to the printing surface, and then the plate is heated to a temperature equal to or higher than the thermal decomposition temperature of the compound of the general formula (1). Can be reproduced on a printing plate and used repeatedly. Furthermore, using the direct drawing function of the ink jet system, a printing plate can be prepared by directly drawing a print manuscript prepared on a computer, and a simple plate making printing method such as on-press plate making can be realized. it can.

[0026]

Embodiments of the present invention will be described below in detail. [Printing Plate Material] As described above, any printing plate material that can be used in the present invention can be used as long as the surface is hydrophilic. Original plate materials having a hydrophilic surface include, for example, a metal plate that has been subjected to a hydrophilic treatment, a paper or plastic support provided with a hydrophilic resin device, a glass substrate, a metal oxide that itself is hydrophilic, and a surface hydrophilic treatment. Metal oxides and the like are given, and solid materials having a so-called photocatalytic ability, whose surface becomes hydrophilic upon irradiation with actinic light, are particularly preferable. The substance having photocatalytic activity preferably used in the present invention is not necessarily limited to metal oxides. However, in consideration of requirements as a printing original plate, preferable substances are often found in metal oxides. This material is also found in ceramics and semiconductors. Ceramics with photocatalytic properties are composed of composite metal oxides.Most semiconductors with photocatalytic properties are genuine semiconductors, whose base order and conductor are close, and pseudo semiconductors such as vanadium oxide and copper oxide, which depend on impurity levels. And is seen in both. Since these ceramics and semiconductors are the same as other metal oxides having photocatalytic ability on the photocatalytic ability utilized by the present invention, they will be described below by including them in "metal oxide having photocatalytic ability". .

Preferred substances having photocatalytic activity belong to the group consisting of oxides of metals belonging to the third to sixth periods of the periodic table and selected from elements other than groups 0 and VIIA (halogen elements). It consists of at least one. Among them, TiO ₂ , RTiO ₃ (R is an alkaline earth metal atom), AB _2-x C _x D _3-x E _x O
₁₀ (A is a hydrogen atom or an alkali metal atom, B is an alkaline earth metal atom or a lead atom, C is a rare earth atom, D is a metal atom belonging to the group 5A element of the periodic table, and E is a metal atom belonging to the same group 4A element. Atom, x represents any numerical value from 0 to 2), SnO ₂ , Bi ₂ O ₃ , ZnO, ZrO, GeO
₂ and a metal oxide selected from FeO _y (y = 1.0 to 1.5) are preferred.

These metal oxides are found in various forms of metal oxides, and may be single metal oxides or composite oxides. In the latter case, solid solutions, mixed crystals, polycrystals, A mixture having a crystal property, an amorphous solid solution, and a metal oxide microcrystal has this property.

The metal and metal oxide having photocatalytic activity that can be used in the present invention must not be excessively dissolved in fountain solution when used as a printing plate.
The solubility in water is 1 for 100 ml of water.
0 mg or less, preferably 5 mg or less, more preferably 1 mg or less
mg or less.

The individual metal oxides having photocatalytic ability will be described. Among the metal oxides, titanium oxide and zinc oxide are preferable, and these will be described first. Any of these can be used as the printing plate material of the present invention. In particular, titanium oxide is preferred in terms of sensitivity (that is, sensitivity to surface light change). As the titanium oxide, one made by any known method such as sulfuric acid heating and sintering of ilmenite or titanium slag, or heat chlorination followed by oxygen oxidation can be used. Alternatively, as described later, a method of forming an oxide film by vacuum evaporation at the stage of producing a printing plate using titanium metal can also be used.

In order to provide a layer containing titanium oxide or zinc oxide on the surface of the master plate, for example, a method of coating a dispersion of titanium oxide microcrystals or zinc oxide microcrystals on a printing plate base plate is used. A method of reducing or removing the binder by baking afterwards, a method of providing a titanium oxide (or zinc oxide) film on a printing original plate by a method such as vapor deposition, sputtering, ion plating, or CVD, for example, a titanium organic compound such as titanium butoxide Can be applied to the original plate and then subjected to firing oxidation to form a titanium oxide layer, or any other known method. In the present invention, a titanium oxide layer formed by vacuum evaporation or sputtering is particularly preferred.

The above or the method of applying the titanium oxide microcrystals is, specifically, a method of applying an amorphous titanium oxide microcrystal dispersion, followed by firing to form an anatase or rutile type titanium oxide layer. A method of applying a mixed dispersion of titanium oxide and silicon oxide to form a surface layer, and a method of applying a mixture of titanium oxide and organosiloxane to obtain a titanium oxide layer bonded to a support through a siloxane bond A method of dispersing and applying a polymer binder capable of coexisting with an oxide in an oxide layer, followed by baking to remove an organic component. As the binder for the oxide fine particles, a polymer that has dispersibility with respect to the titanium oxide fine particles and can be removed by firing at a relatively low temperature can be used. Examples of preferred binders include polyalkylene such as polyethylene, polybutadiene, polyacrylate, polymethacrylate, polyvinyl acetate, polyvinyl formate, polyethylene terephthalate, polyethylene naphthalate, polyvinyl alcohol, partially saponified polyvinyl alcohol, polystyrene and the like. Is preferred, and these resins may be used as a mixture.

In performing the above-mentioned vacuum deposition of titanium oxide,
Is usually used as a heat source for evaporation heating in vacuum evaporation equipment.
And place it in a vacuum of 10^-6-10^-3Total gas pressure at 10 Pa^-3
-10 ⁰Pa, so that the oxygen pressure ratio becomes 30-90%
While evaporating titanium metal, oxidation surface is oxidized
A deposited thin film of titanium is formed. Also, sputtering
In the case of using a titanium metal tar
Set get and Ar / O_TwoThe ratio is 60/40 (mol
After adjusting the gas pressure to 0.5 Pa so that
Apply RF power 200W and perform sputtering
A titanium oxide thin film is formed on a substrate.

On the other hand, when a zinc oxide layer is used in the present invention, the zinc oxide layer can be formed by any known method. In particular, a method of forming an oxide film by electrolytic oxidation of the surface of a metal zinc plate and a method of forming a zinc oxide film by vacuum deposition, sputtering, ion plating, CVD, or the like are preferable. A method of forming a zinc oxide film by depositing metal zinc in the presence of oxygen gas in the same manner as the above-described titanium oxide deposition, or a method of forming a zinc metal film in the absence of oxygen, followed by air In the temperature of about 70
A method of raising the temperature to 0 ° C. and oxidizing can be used.
In addition, it can be obtained by heating a coating layer of zinc oxalate or a thin layer of zinc selenide in an oxidizing gas stream.

The thickness of the deposited film is preferably 1 to 10000 nm, and more preferably 1 to 1000 nm, for both the titanium oxide layer and the zinc oxide layer. More preferably 300n
It is preferable to prevent the distortion of the optical interference by setting m or less. Further, it is convenient that the thickness is 5 nm or more in order to sufficiently exhibit the photoactivation effect.

As the titanium oxide, any crystal form can be used, but an anatase type is particularly preferred because of its high sensitivity. It is well known that anatase-type crystals can be obtained by selecting firing conditions in the process of firing titanium oxide. In this case, amorphous titanium oxide or rutile-type titanium oxide may coexist, but those containing 40% or more, preferably 60% or more of anatase-type crystals are preferable for the above reason. The volume ratio of titanium oxide or zinc oxide in the layer mainly containing titanium oxide or zinc oxide is 30 to 100%, preferably 50 to 100%.
% Or more is preferably occupied by the oxide, more preferably a continuous layer of oxide, ie substantially 100%.
However, since the surface hydrophilicity / lipophilicity change characteristics are not affected by remarkable purity as when zinc oxide is used in an electrophotographic photosensitive layer, a material having a purity close to 100% (for example, 98%) is further purified. There is no need to convert. That is, it can be understood from the fact that the physical properties used in the present invention are the properties of changing the hydrophilic / lipophilic properties of the membrane surface, which are not related to the conductivity, that is, the properties of changing the properties of the interface.

However, it may be effective to dope a certain metal in order to enhance the property of changing the hydrophilicity of the surface by the action of light, and for this purpose, doping of a metal having a low ionization tendency is suitable. And
It is preferable to dope Pt, Pd, Au, Ag, Cu, Ni, Fe, Co or Cr. Further, a plurality of these preferable metals may be doped. Also in the case where doping is performed, the injection amount is 5 mol% or less based on the metal components in zinc oxide and titanium oxide.

On the other hand, when the volume ratio is low, the hydrophilicity /
The sensitivity of the lipophilic light response behavior decreases. Therefore,
The volume ratio of the oxide in the layer is desirably 30% or more, particularly preferably substantially 100%.

Next, a metal titanate represented by the general formula RTiO ₃ which is another compound usable in the present invention will be described. In the general formula RTiO ₃ , R is a metal atom belonging to an alkaline earth element of the periodic table such as magnesium, calcium, strontium, barium, beryllium, and particularly preferably strontium and barium. Also, two or more alkaline earth metal atoms can coexist as long as the total thereof is stoichiometrically consistent with the above formula.

Next, the general formula AB _2-x C _x D _3-x E _x O ₁₀
The compound represented by is described. In the general formula, A is a monovalent atom selected from a hydrogen atom and an alkali metal atom such as sodium, potassium, rubidium, cesium, and lithium. More than one species may coexist. B
Is an alkaline earth metal atom or a lead atom as defined above for R, and two or more kinds of atoms may coexist as long as they are stoichiometrically matched. C is a rare earth atom, preferably scandium and yttrium, and lanthanum, cerium, praseodymium, neodymium, holmium, europium, gadolinium, terbium, lanthanide elements such as thulium, ytterbium, lutetium, etc. May coexist as long as stoichiometrically matches the above formula. D is one or more elements selected from Group 5A elements of the periodic table, and includes vanadium, niobium, and tantalum. Further, as long as the stoichiometric relationship is satisfied, two or more kinds of 5A group metal atoms may coexist. E is a metal atom belonging to a Group 4A element such as titanium, zirconium, or hafnium, and two or more kinds of Group 4A metal atoms may coexist. x represents an arbitrary numerical value of 0 to 2.

RTiO ₃ , general formula AB _2-x C _x D _3-x E
The compound represented by _{x O 10, SnO 2, Bi} 2 O 3,
The above-described method of providing titanium oxide and zinc oxide can be used for forming any thin film of an iron oxide-based compound represented by ZrO, GeO _2, and FeO _y (y = 1.0 to 1.5). That is, a method of applying a dispersion of fine particles of metal oxide on a printing plate precursor, a method of applying and baking to reduce or remove the binder, and applying various types of vacuum to the printing plate precursor by applying the above-mentioned oxide to the printing plate. A method of forming a film by a thin film method,
For example, a method in which an organic compound such as an alcoholate of a metal element is applied onto a base plate, then hydrolyzed, and further baked and oxidized to form a metal thin film having an appropriate thickness, and an aqueous solution of a hydrochloride or a nitrate of the metal element. Any known method such as a method of heating and spraying can be used.

For example, in order to apply the barium titanate fine particles by the application method described above, a method of applying a mixed dispersion of barium titanate and silicon to form a surface layer, barium titanate and organopolysiloxane Alternatively, there is a method of applying a mixture with the monomer. Further, as described in the section of titanium oxide, the oxide layer can be formed by dispersing and applying a polymer binder which can coexist with the oxide in the oxide layer, followed by firing. Examples of preferred polymers as the binder for the oxide fine particles are the same as those described in the section of the titanium oxide layer. By this method, a thin film of magnesium titanate, calcium titanate, strontium titanate or an intermolecular compound or a mixture thereof can be similarly formed in addition to barium titanate.

Similarly, according to the coating method described above,
CsLa_TwoNbTi_TwoO_TenFine particles can be applied
It is. CsLa_TwoNbTi_TwoO_TenThe fine particles, their chemical
Cs corresponding to stoichiometry_TwoCO_Three, La_TwoO_Three, NbO_Five, TiO
_TwoPulverize in a mortar and put in a platinum crucible, 130 ° C
Bake for 5 hours, cool it and put in a mortar
Pulverize to fine particles less than cron. This CsLa_TwoNbT
i_TwoO_TenThe fine particles are converted into particles in the same manner
And then applied to form a thin film. This one
The law is CsLa_TwoNbTi_TwoO_TenH
Ca_1.5La₀₅ Nb_2.5Ti_0.5O_Ten, HLa_TwoNbT
i_TwoO_TenAB mentioned above_2-xC_xD_3-x E_xO_Ten, (0
≦ x ≦ 2).

As a method for forming a metal oxide layer having a photocatalytic ability or a high-temperature hydrophilicity developing property using the above-described vacuum thin film forming method, a sputtering method or a vacuum thin film forming method is generally used. In the sputtering method, a single or composite oxide target is prepared in advance. For example, a barium titanate crystal thin film can be obtained by performing RF sputtering in an argon / oxygen mixed atmosphere while maintaining the temperature of the support for the deposited film at 450 ° C. or higher using a barium titanate target. For controlling the crystallinity, post-annealing is required to be 300 to 90 if necessary.
What is necessary is just to carry out at 0 degreeC. In this method, a thin film can be formed on the aforementioned RTiO ₃ (R is an alkaline earth metal atom) and other metal oxides by adjusting the substrate temperature optimal for controlling the crystal in the same manner. For example, when a tin oxide thin film is provided, the substrate temperature is 120 ° C., and the argon / oxygen ratio is 5
By performing RF sputtering in a mixed atmosphere of 0/50, a thin film of a tin oxide crystal for the purpose is obtained.

Method using the above metal alcoholate
Also, the desired thin film can be formed without using a binder
Is the way. To form a barium titanate thin film
Mixed alcohol of lium ethoxide and titanium butoxide
Solution on the surface with SiO_TwoOn a silicon substrate with
Cloth and after hydrolyzing the surface, to 200 ° C or more
Can be heated to form barium titanate thin film
It is. The method of this method is also similar to the other RTiO described above._Three(R is
Alkaline earth metal atom), AB_2-xC_xD_3-xE _xO_Ten
(A, B, C, D, and E represent the contents of the above definitions, respectively.
), SnO_Two, SiO_Two, Bi_TwoO_Three, ZrO, Ge
O_TwoAnd FeO_yOxidation represented by (y = 1.0-1.5)
It can be applied to the formation of a thin film of an iron-based compound.

The method for forming a metal oxide thin film as described above can also form a binder-free thin film. In order to form a thin film of SnO _2, an aqueous solution of hydrochloric acid of SnCl ₄ can be sprayed onto the surface of quartz or crystalline glass heated to 200 ° C. or higher to form a thin film. In this method, in addition to the SnO ₂ thin film, the aforementioned RTiO ₃ (R
Is an alkaline earth metal atom), AB _2-x C _x D _3-x E _x O
₁₀ (A, B, C, D and E respectively represent the contents of the above definition), Bi ₂ O ₃ , ZrO, GeO ₂ and FeO _y (y =
1.0 to 1.5, for example, ferrite, triiron tetroxide, ferric oxide, etc.).

In any of the above cases, the thickness of the metal oxide thin film is preferably 1 to 10000 nm, and more preferably 10 to 10000 nm.
000 nm. It is more preferable that the thickness be 300 nm or less to prevent distortion of optical interference. Further, it is convenient that the thickness is 5 nm or more in order to sufficiently exhibit the photoactivation effect.

In the case where the binder is used, the volume ratio of the metal oxide in the thin layer of the metal oxide having photocatalytic ability is 50 to 100%, preferably 90% or more. More preferably, it is a continuous layer of oxide, that is, substantially 100%.

In addition, ZnO, TiO ₂ , SnO ₂ , Z
rO, GeO ₂ , ZrO, GeO ₂ and FeO _y (y = 1.
The iron oxide-based compounds represented by 0 to 1.5) can also be obtained by anodizing the surface of each metal plate. In particular, ZnO and TiO ₂ can be easily obtained by anodic oxidation as an oxide film having a photocatalytic function with a support. Anodizing method is described in, for example, JP-A-6-3
No. 5,174, pages 3-5, the method cited therein, the method described in JP-A-52-37104, and the anode of an aluminum support for a printing plate of the present invention. The oxidation is carried out by a known suitable method such as the method described below, or a method analogous thereto. When the raw material is made by anodic oxidation, the thickness of the oxide film may be the above-described thickness, but may be even larger,
It is used at 2.0 microns or less, preferably at 1.0 microns or less.

[Form of Printing Original] Next, the form of the printing original used in the present invention will be described. Various forms and materials can be used for the printing plate according to the present invention. For example, a method in which a thin layer of a photocatalytic substance or another surface hydrophilic substance is directly provided on the surface of a substrate of a plate cylinder of a printing press by the above-described method such as vapor deposition, immersion or coating, a photocatalytic substance supported on a support. Alternatively, a printing method can be used in which a thin plate of a surface hydrophilic substance or the above-mentioned substance having no support is wound around a substrate of a plate cylinder to form a printing plate. Also, of course, in addition to the above-mentioned form of making a plate on a plate cylinder,
As is generally practiced, a printing plate that has undergone plate making may be mounted on a rotary or flatbed printing press.

When a substance having a photocatalytic function or an image-forming layer having a surface hydrophilic substance is provided on a support, the support used for the present invention contains a compound of the general formula (1). A dimensionally stable plate that can carry an ink image, and is preferably a metal plate such as an aluminum plate, a SUS steel plate, a nickel plate, or a copper plate, and particularly preferably uses a flexible metal plate. Is preferred. Also,
Flexible plastic supports such as polyesters and cellulose esters can also be used. An oxide layer may be provided on a support such as waterproofed paper, polyethylene laminated paper, or impregnated paper, and it may be used as a printing plate. Such a support is also preferably used when a substance having photocatalytic ability is provided on the support.
In the case of using an electrostatic discharge type ink jet apparatus in which ink droplets are charged, a known suitable conductive layer is provided between the image forming layer surface or the image forming layer and the support, or an amine, It is desirable to impregnate inorganic or organic salts to impart conductivity. In the case of a metal plate support such as an aluminum plate, the substrate itself is conductive, and any type of ink jet device can be applied.

Specifically, paper, paper laminated with a plastic sheet (eg, a sheet of polyethylene terephthalate, polyimide, etc.), a metal plate (eg, aluminum, zinc, copper, stainless steel, etc.), plastic film (eg, Cellulose acetate, cellulose triacetate,
Cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyimide, polystyrene, polycarbonate, polyvinyl acetal, etc.), the above-mentioned metal-laminated or evaporated paper, or plastic film.

A preferred support is a polyester film, a polyimide film, aluminum, or a SUS plate which is hardly corroded on a printing plate. Among them, an aluminum plate and a film which have good dimensional stability and are relatively inexpensive are particularly preferable.

A preferred polyimide film is a polyimide resin film obtained by polymerizing pyromellitic anhydride and m-phenylenediamine and then performing cyclic imidization.
This film is commercially available (for example, “Kapton” manufactured by Dupont Toray) can be mentioned.

Suitable aluminum plates are a pure aluminum plate and an alloy plate containing aluminum as a main component and a trace amount of a different element, and may be a plastic film on which aluminum is laminated or vapor-deposited. The foreign elements contained in the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, and titanium. The content of the foreign element in the alloy is at most 10% by weight or less. Particularly preferred aluminum in the present invention is pure aluminum. However, completely pure aluminum is difficult to produce due to refining technology, and therefore may contain a slightly different element. As described above, the composition of the aluminum plate applied to the present invention is not specified, and an aluminum plate of a conventionally known and used material can be appropriately used. The thickness of the metal support used in the present invention is about 0.1 mm to 0.6 mm, preferably 0.15 mm to 0.4 mm, particularly preferably 0.2 mm
The thickness of other supports such as plastic and processed paper is about 0.1 mm to 2.0 mm, preferably 0.2 mm to 1.0 mm.

When an aluminum support is used, it is preferable to use a roughened surface. In this case, if desired, a degreasing treatment with a surfactant, an organic solvent, an alkaline aqueous solution, or the like is performed to remove the rolling oil on the surface prior to the surface roughening. The surface roughening treatment of the surface of the aluminum plate is performed by various methods, for example, a method of mechanically roughening the surface, a method of electrochemically dissolving the surface, and a method of selectively dissolving the surface chemically. It is performed by the method of causing. As a mechanical method, a known method such as a ball polishing method, a brush polishing method, a blast polishing method, and a buff polishing method can be used. In addition, as the electrochemical surface roughening method, a known method such as performing an alternating or direct current in a hydrochloric acid or nitric acid electrolyte can be used. Further, the roughened aluminum plate is subjected to an alkali etching treatment and a neutralization treatment as necessary, and then subjected to an anodic oxidation treatment if necessary to increase the water retention and abrasion resistance of the surface. The concentration of the electrolyte for anodic oxidation is appropriately determined depending on the type of the electrolyte.

The anodizing treatment conditions vary depending on the electrolyte used and cannot be specified unconditionally. However, in general, the concentration of the electrolyte is 1 to 80% by weight, the solution temperature is 5 to 70 ° C.,
It is appropriate that the current density is 5 to 60 A / dm ² , the voltage is 1 to 100 V, and the electrolysis time is 10 seconds to 5 minutes. If the amount of the anodic oxide film is less than 1.0 g / m ² , the printing durability is insufficient or the non-image area of the lithographic printing plate is easily scratched, and the ink adheres to the scratched area during printing. So-called "scratch dirt"
Tends to occur.

The structure of the printing plate using the photocatalytic substance used in the printing method of the present invention has been described above. Next, the surface of the photocatalytic substance which is particularly preferable as the printing plate used in the present invention is described. The front hydrophilicity will be described.

When the printing original plate is made of a material having photocatalytic ability, the surface is irradiated with active light in an image-wise manner to form a hydrophilic region. As described above, the hydrophilicization is not necessarily performed prior to the writing of the hydrophobic image by the ink jet method, and the drawing may be performed first. However, the method of the hydrophilicity does not change in any case. The light source is a light source that emits light having a wavelength in a photosensitive region of a substance having photocatalytic ability, that is, light having a wavelength corresponding to a light absorption region. For example, when the substance having photocatalytic ability is titanium oxide, the anatase type is 387 nm or less, the rutile type is 413 nm or less, the zinc oxide is 387 nm or less, and in the case of many other metal oxides, it is exposed to ultraviolet light of 250 to 390 nm. In the case of zinc oxide,
In addition to the intrinsic absorption wavelength range (ultraviolet range), spectral sensitization can be performed in a known manner to broaden the applicable wavelength range of the active light, so that the light source used emits light in these wavelength ranges. It is a light source and can be said to be a light source that mainly emits ultraviolet light. Means for forming an imagewise distribution of the hydrophilic region by the photocatalytic action of the active light may be any of a surface exposure method and a scanning method.

In the case of the surface exposure method, uniform light is irradiated onto the original plate to make the surface of the irradiated area hydrophilic.
When the support is transparent, exposure can be performed through the support from the back side of the support. Light sources suitable for irradiating the active light by the surface exposure method include a mercury lamp, a tungsten halogen lamp, other metal halide lamps, and a xenon discharge lamp. The exposure time is determined in consideration of the exposure illuminance so as to obtain the above exposure intensity.

The preferred intensity of the irradiation light varies depending on the properties of the image forming layer of the photocatalytic metal oxide, and also depends on the wavelength of the active light, the spectral distribution and the light absorption of the substance having photocatalytic ability. Surface exposure intensity of 0.05 to 10
0 joule / cm ² , preferably 0.05 to 10 jo
ule / cm ² , more preferably 0.05 to 5 joul
e / cm ² . In addition, a reciprocity law is often established in the photocatalytic reaction. For example, the same effect can be obtained by performing exposure at 10 mW / cm ² for 100 seconds or exposure at 1 W / cm ² for 1 second. In such a case, the range of selection of the light source that emits the active light is widened.

The irradiation of active light is performed by a scanning exposure method.
If not, the laser beam is converted into a time-series electrical signal.
Scanning exposure is performed as one-dimensional or two-dimensional irradiation light. Les
The laser light source is a known laser that oscillates a beam of active light.
Can be used. For example, an oscillation wave
A helium-cadmium laser having a length of 325 nm,
A water-cooled laser having an oscillation wavelength of 351.1 to 363.8 nm
Lugon laser, zinc sulfide with 330-440nm
/ A cadmium laser or the like can be used. Further
UV laser and near-ultraviolet laser oscillation were confirmed
Gully nitride having an oscillation wavelength of 360 to 440 nm
-Based InGaN-based quantum well semiconductor laser and laser
Waveguide MgO-L having oscillation wavelength of 360 to 430 nm
iNb0 _ThreeUse an inverted domain wavelength conversion type laser.
You can also. Laser output of 0.1-300W
Irradiation can be performed by a user. Also, pulsed laser
-If the peak output is 1000W,
Preferably, a laser beam of 2000 W is irradiated. Branch
If the support is transparent, pass the support from behind the support.
And can be exposed. By irradiation of the laser term
When making hydrophilic, unlike drawing,
The diameter of the beam does not have to be narrowed down and is optional,
A beam diameter of about 10 to 100 μm is preferable.
No.

[Formation of Hydrophobic Image Area] In the printing method of the present invention, drawing is performed by an ink jet apparatus using a liquid containing a hydrophobic liquid containing a compound of the general formula (1) as ink. When the compound-containing solution of the general formula (1) comes into contact with the surface of the printing plate (image recording surface), it usually reacts with the hydroxyl group on the surface of the printing plate, and passes through oxygen to form the surface of the printing plate (image recording). Surface) or is adsorbed on the surface of the printing plate (image recording surface) to form a lipophilic layer on the surface of the printing plate with the compound of the formula (1). And
The printing original plate surface (image recording surface) provided with the lipophilic layer forms an image region, and the hydrophilic surface region forms a non-image portion.

The compound of the general formula (1) having the above function used in the present invention is represented by the following general formula (1). G _n JM _4-n (1) In the compound of the general formula (1), G represents a lipophilic organic group, and J represents an element having a valence of 4 selected from C, Si, Ge, Ti, Zr and Sn. And M represents a halogen or an alkoxy group, and n represents an integer of 1 to 3. As described above, when the compound of the general formula (1) is in contact with the surface of the image recording layer of the photosensitive lithographic printing plate, M is hydrolyzed by water in the air to be hydroxylated, and the hydroxyl group on the surface of the image recording layer is converted. The lipophilic organic group G forms a lipophilic layer on the surface of the image recording layer due to the dehydration reaction and the bonding or adsorption to the surface of the image recording layer via oxygen. When the image recording layer provided with the lipophilic layer is imagewise heated, the bond between the compound of the general formula (1) in the heated portion and the image recording layer (that is, (metal atoms of the image recording layer) −
The bond between oxygen and J or the bond included in G _n J in the bond (oxygen-J atom bond) is broken, or the adsorption between the compound of the general formula (1) and the image recording layer is desorbed. The compound of the general formula (1) is desorbed or decomposed and removed, and the heated portion is hydrophilized. The polarity conversion in a state where the compound of the general formula (1) is adsorbed is significantly larger than the polarity conversion by heating the image recording layer. The lipophilic organic group G is not particularly limited as long as it can impart the above function to the compound of the general formula (1) and can fulfill the function of forming the main lipophilic layer. Specifically, examples of the lipophilic organic group G include an alkyl group or an aryl group having preferably 1 to 32 carbon atoms, more preferably 3 to 18 carbon atoms, and a hydrogen atom of the alkyl group or the aryl group. Is an aryl group, a halogen atom, an epoxy group, an amino group, a vinyl group, a vinyl group, a methacryloxy group, a cyano group, an alkylthio group (for example,
An alkyloxy group (for example, having 1 carbon atom)
To 8) and the like.

More specifically, an alkyl group (methyl group,
Ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group,
Undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, etc., monochloroalkyl group (3-chloropropyl group,
Chloromethyl group, 4-chlorobutyl group, 2-chloroethyl group, 5-chloropentyl group, 6-chlorohexyl group, etc., polychloroalkyl group (3,3,3-trichloropropyl group, trichloromethyl group, trichlorobutyl group) , Trichloroethyl group, trichloropentyl group, 3,
3,4,4,5,5,6,6,6-nonachlorohexyl group), acetoxymethyl group, acetoxypropyl group,
4-aminobutyl group, benzyl group, aminoethyl group, aminopropyl group, 3-aminophenoxy group, 5- (bicycloheptenyl) group, ureapropyl group, vinylbenzyloxy group, thienyl group, phenylthienyl group, phenoxypropyl Group, vinyl group, butenyl group, octenyl group, octadienyl group, morpholinopropyl group, morpholinoethylthiopropyl group, N-methylaminopropyl group, methoxyphenyl group, methacryloxymethyl group, O
-Methacryloxy (polyethyleneoxy) ethyl group, ethylmethylketoximinomethyl group, 5,6-epoxyhexyl group, γ-glycidoxypropyl group, epoxyethyl group, epoxymethyl group, glycidyl group, 2- (3,4
-Epoxycyclohexyl) group, docosenyl group, o-tolyl group, p-tolyl group, pyridino group, diethylphosphateethyl group, N, N-diethyl-3-aminopropyl group, cyclohexyl group, 2- (3-cyclohexenyl)
Ethyl group, 3-cyanopropyl group, chloropropyl group,
And a 2- (carboxymethylthio) ethyl group.

J is C, Si, Ge, Ti, Zr and Sn
And an element having a valence of 4 selected from the following. When the main component of the image recording layer is titanium oxide, J is preferably C or Ti in that the photosensitive lithographic printing plate is particularly excellent in reproduction performance. M represents a halogen atom or an alkoxy group. As the halogen atom, chlorine, bromine, iodine and fluorine are particularly preferable, and chlorine is preferable. The alkoxy group preferably has 1 to 12 carbon atoms, and more preferably has 3 to 6 carbon atoms. When n is 1 or 2, a plurality of M may be substituted with the same or different halogen atoms and / or alkoxy groups. n
Is an integer of 1 to 3, and is preferably 1.

Specific examples of the compound of the general formula (1) include:
Methyltrichlorosilane, ethyltrichlorosilane, propyltrichlorosilane, butyltrichlorosilane, pentyltrichlorosilane, hexyltrichlorosilane,
Heptyltrichlorosilane, octyltrichlorosilane, nonyltrichlorosilane, decyltrichlorosilane, undecyltrichlorosilane, dodecyltrichlorosilane, tridecyltrichlorosilane, tetradecyltrichlorosilane, pentadecyltrichlorosilane, hexadecyltrichlorosilane, heptadecyltrichlorosilane, Octadecyltrichlorosilane, nonadecyltrichlorosilane, eicosyltrichlorosilane,

Dimethyldichlorosilane, ethylmethyldichlorosilane, propylmethyldichlorosilane, butylmethyldichlorosilane, pentylmethyldichlorosilane, hexylmethyldichlorosilane, heptylmethyldichlorosilane, octylmethyldichlorosilane, nonylmethyldichlorosilane, decylmethyldichlorosilane Chlorosilane,
Undecylmethyldichlorosilane, dodecylmethyldichlorosilane, tridecylmethyldichlorosilane, tetradecylmethyldichlorosilane, pentadecylmethyldichlorosilane, hexadecylmethyldichlorosilane, heptadecylmethyldichlorosilane, octadecylmethyldichlorosilane, nonadecylmethyldi Chlorosilane, eicosylmethyldichlorosilane, trimethylchlorosilane, ethyldimethylchlorosilane, propyldimethylchlorosilane, butyldimethylchlorosilane, pentyldimethylchlorosilane, hexyldimethylchlorosilane,
Heptyldimethylchlorosilane, octyldimethylchlorosilane, nonyldimethylchlorosilane, decyldimethylchlorosilane, undecyldimethylchlorosilane, dodecyldimethylchlorosilane, tridecyldimethylchlorosilane, tetradecyldimethylchlorosilane, pentadecyldimethylchlorosilane, hexadecyldimethylchlorosilane, heptadecyldimethylchlorosilane, Octadecyldimethylchlorosilane, nonadecyldimethylchlorosilane, eicosyldimethylchlorosilane,

Acetoxymethyltrichlorosilane, acetoxyethyltrichlorosilane, acetoxypropyltrichlorosilane, acetoxybutyltrichlorosilane,
Acetoxypentyltrichlorosilane, acetoxyhexyltrichlorosilane, acetoxyheptyltrichlorosilane, acetoxyoctyltrichlorosilane, acetoxynonyltrichlorosilane, acetoxydecyltrichlorosilane, acetoxyundecyltrichlorosilane,
Acetoxydodecyltrichlorosilane, acetoxytridecyltrichlorosilane, acetoxytetradecyltrichlorosilane, acetoxypentadecyltrichlorosilane, acetoxyhexadecyltrichlorosilane, acetoxyheptadecyltrichlorosilane, acetoxyoctadecyltrichlorosilane, acetoxynonadecyltrichlorosilane, acetoxyeicosyltri Chlorosilane,

[0070] Methyltriethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, butyltriethoxysilane, pentyltriethoxysilane, hexyltriethoxysilane, heptyltriethoxysilane, octyltriethoxysilane, nonyltriethoxysilane, decyltriethoxysilane Ethoxysilane, undecyltriethoxysilane, dodecyltriethoxysilane, tridecyltriethoxysilane, tetradecyltriethoxysilane, pentadecyltriethoxysilane, hexadecyltriethoxysilane, heptadecyltriethoxysilane,
Octadecyltriethoxysilane, nonadecyltriethoxysilane, eicosyltriethoxysilane, dimethyldiethoxysilane, ethylmethyldiethoxysilane, propylmethyldiethoxysilane, butylmethyldiethoxysilane, pentylmethyldiethoxysilane, hexylmethyldiethoxy Silane, heptylmethyldiethoxysilane, octylmethyldiethoxysilane, nonylmethyldiethoxysilane, decylmethyldiethoxysilane, undecylmethyldiethoxysilane, dodecylmethyldiethoxysilane, tridecylmethyldiethoxysilane, tetradecylmethyldi Ethoxysilane, pentadecylmethyldiethoxysilane, hexadecylmethyldiethoxysilane, heptadecylmethyldiethoxysilane, octadecylmethyldiethoxy Shishiran, nonadecyl methyl diethoxy silane, eicosyl methyldiethoxysilane,

Trimethylethoxysilane, ethyldimethylethoxysilane, propyldimethylethoxysilane,
Butyl dimethyl ethoxy silane, pentyl dimethyl ethoxy silane, hexyl dimethyl ethoxy silane, heptyl dimethyl ethoxy silane, octyl dimethyl ethoxy silane, nonyl dimethyl ethoxy silane, decyl dimethyl ethoxy silane, undecyl dimethyl ethoxy silane, dodecyl dimethyl ethoxy silane, tridecyl dimethyl ethoxy Silane, tetradecyldimethylethoxysilane, pentadecyldimethylethoxysilane, hexadecyldimethylethoxysilane, heptadecyldimethylethoxysilane, octadecyldimethylethoxysilane,
Nonadecyldimethylethoxysilane, eicosyldimethylethoxysilane,

3-chloropropyltrichlorosilane, chloromethylmethyldichlorosilane, 4-chlorobutyldimethylchlorosilane, 2-chloroethyltrichlorosilane, 5-chloropentylmethyldichlorosilane, 6-chlorohexyldimethylchlorosilane, 3,3,3 -Trichloropropyltrichlorosilane, trichloromethyldimethylchlorosilane, trichlorobutylmethyldichlorosilane, trichloroethyltrichlorosilane, trichloropentyltrichlorosilane, 3,3,4,4,5
5,6,6,6-nonachlorohexyltrichlorosilane, acetoxymethyltrichlorosilane, acetoxypropyldimethylchlorosilane, 4-aminobutyltrichlorosilane, benzylmethyldichlorosilane, aminoethyldimethylchlorosilane, aminopropylmethyldichlorosilane, 3-amino Phenoxytrichlorosilane,
5- (bicycloheptenyl) trichlorosilane, ureapropyltrichlorosilane, vinylbenzyloxytrichlorosilane, thienyltrichlorosilane, phenylthienyldimethylchlorosilane, phenoxypropyltrichlorosilane, vinyldimethylchlorosilane, butenylmethyldichlorosilane, octenyldimethylchlorosilane,
Octadienyltrichlorosilane, morpholinopropyldimethylchlorosilane, morpholinoethylthiopropyldimethylchlorosilane, N-methylaminopropylmethyldichlorosilane, methoxyphenylmethyldichlorosilane, methacryloxymethylmethyldichlorosilane, O-methacryloxy (polyethyleneoxy) ethyl Dimethylchlorosilane, ethylmethylketoximinomethyltrichlorosilane, 5,6-epoxyhexyldimethylchlorosilane, γ-glucidopropylmethyldichlorosilane, epoxyethyltrichlorosilane, epoxymethyldimethylchlorosilane, glycidylmethyldichlorosilane, 2- (3 4-epoxycyclohexyl) trichlorosilane, docosenyltrichlorosilane, o-tolylmethyldichlorosilane Emissions, p- tolyl methyldichlorosilane, pyridinoporphyrazine methyldichlorosilane, diethyl phosphate ethyl trichlorosilane, N, N-diethyl -3
-Aminopropyldimethylchlorosilane, cyclohexyldimethylchlorosilane, 2- (3-cyclohexenyl) ethyldimethylchlorosilane, 3-cyanopropyldimethylchlorosilane, chloropropyltrichlorosilane, 2- (carboxymethylthio) ethylmethyldichlorosilane, vinyltrichlorosilane, vinyl Triethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, β (3,4 epoxy synchrohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldi Ethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-
β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N
-Phenyl-γ-aminopropyltrimethoxysilane,
γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane,

3-chloropropyltriethoxysilane,
Chloromethylmethyldiethoxysilane, 4-chlorobutyldimethylethoxysilane, 2-chloroethyltriethoxysilane, 5-chloropentylmethyldiethoxysilane, 6-chlorohexyldimethylethoxysilane, 3,
3,3-trichloropropyltriethoxysilane, trichloromethyldimethylethoxysilane, trichlorobutylmethyldiethoxysilane, trichloroethyltriethoxysilane, trichloropentyltriethoxysilane,
3,3,4,4,5,5,6,6,6-nonachlorohexyltriethoxysilane, acetoxymethyltriethoxysilane, acetoxypropyldimethylethoxysilane, 4-aminobutyltriethoxysilane, benzylmethyldiethoxysilane , Aminoethyldimethylethoxysilane, aminopropylmethyldiethoxysilane, 3-
Aminophenoxytriethoxysilane, 5- (bicycloheptenyl) triethoxysilane, ureapropyltriethoxysilane, vinylbenzyloxytriethoxysilane, thienyltriethoxysilane, phenylthienyldimethylethoxysilane, phenoxypropyltriethoxysilane, vinyldimethylethoxy Silane, butenylmethyldiethoxysilane, octenyldimethylethoxysilane, octadienyltriethoxysilane, morpholinopropyldimethylethoxysilane, morpholinoethylthiopropyldimethylethoxysilane, N-methylaminopropylmethyldiethoxysilane, methoxyphenyl Methyldiethoxysilane, methacryloxymethylmethyldiethoxysilane, O-methacryloxy (polyethyleneoxy) ethyldi Chill silane, ethyl methyl keto creaking Roh methyltriethoxysilane, 5,6-epoxy hexyl dimethyl silane, epoxy ethyl triethoxysilane, epoxy methyl dimethyl silane, glycidyl methyl diethoxy silane, 2-
(3,4-epoxycyclohexyl) triethoxysilane, docosenyltriethoxysilane, o-tolylmethyldiethoxysilane, p-tolylmethyldiethoxysilane, pyridinomethyldiethoxysilane, diethylphosphateethyltriethoxysilane, N, N-diethyl-
3-aminopropyldimethylethoxysilane, cyclohexyldimethylethoxysilane, 2- (3-cyclohexenyl) ethyldimethylethoxysilane, 3-cyanopropyldimethylethoxysilane, chloropropyltriethoxysilane, 2- (carboxymethylthio) ethylmethyldiethoxy Silane

N-octadecyltrichloromethane, n-
Octadecyltrichlorotitanium, phenyltrichlorogermane, O-allyloxy (polyethyleneoxy) triisopropoxytitanate, titanium isobutoxide,
Titanium isobutoxide, titanium n-nonyl oxide, zirconium t-butoxide, zirconium n-
Examples thereof include propoxide, tetraisopropoxy tin-isopropanol, and other compounds that can substitute Si with C, Ge, Ti, Zr, and Sn in the reactive silicon compounds exemplified above. Compounds having a structure in which Si is replaced with another element are also highly effective for the purpose of the present invention, and are particularly effective when the metal element is Ti or Zr. Since it is replaced with a non-metallic element, its illustration is omitted.

The compounds of the above formula (1) are used alone or in combination. In addition, as long as they have a structure having groups G, J, and M that exhibit the same function as the compound of the above general formula (1), the compound of the general formula (1) is dehydrated by a dehydration condensation reaction. Oligomerized ones via O bonds may be used. The compound of the general formula (1) is
Commercially available ones can be used, for example, Shin-Etsu Chemical Co., Ltd.
Available from Chisso Corporation.

Since the ink containing the compound of the general formula [1] used in the present invention is intended to form a hydrophobic image-like area, it is a solution of only the compound of the general formula [1] in a hydrophobic solvent. A known inkjet oil such as an organic solvent, a surfactant, an organic polymer compound, a dye or a pigment, etc. is used to optimize the jetting properties, visibility, droplet dispersion, charging characteristics, etc. of the inkjet apparatus. Additives for soluble inks can be added as needed.

In the present invention, any apparatus can be used as long as it is an ink jet apparatus using oil-based ink. As the oil-based ink to be used, a non-aqueous solvent preferably having an electric resistance of 10 ⁹ Ω · cm or more and a dielectric constant of 3.5 or less can be used as a solution or a dispersion medium. If the apparatus is other than the electrostatic discharge type, there is no restriction on the dielectric constant as described above, and the range of choice of the solvent can be widened.

The non-aqueous solvent used in the present invention is preferably a linear or branched aliphatic hydrocarbon, alicyclic hydrocarbon, or aromatic hydrocarbon, and a halogen-substituted hydrocarbon. For example, octane, isooctane, decane, isodecane, decalin, nonane, dodecane, isododecane, cyclohexane, cyclooctane,
Cyclodecane, benzene, toluene, xylene, mesitylene, isoper E, isoper G, isoper H, isoper L (Isoper; trade name of Exxon), Shelsol 70, Shersol 71 (Shersol; trade name of Shell Oil Co.), Amsco OMS, Amsco 46
0 solvent (Amsco; trade name of Spirits) or the like is used alone or in combination. The upper limit of the electric resistance of such a non-aqueous solvent is about 10 ¹⁶ Ω · cm, and the lower limit of the dielectric constant is about 1.8.

The reason why the electric resistance of the non-aqueous solvent used is in the above range is that if the electric resistance is low, the electric resistance of the ink is not appropriate and the ejection of the ink by the electric field is deteriorated. The reason for setting the range is that when the dielectric constant is high, the electric field is easily relaxed in the ink, so that the ejection of the ink is likely to be deteriorated. In the case of using an ink jet device other than the electrostatic discharge type, even if the device uses oil-based ink, there is little restriction on the dielectric constant, and a solvent having a relatively high polarity such as octanol, decanol, and MEK can be used. In order to suppress bleeding after the ink lands as an image, two or more kinds of solvents can be used, or a polymer material described below, a viscosity modifier, or many solvents for controlling an evaporation rate can be added. . Examples of such solvents include alcohols, ethers, acetals, ketones, esters, fatty acids, amines, phenols, and plastic solvents.

In the present invention, since the image area may be formed by the image-like portion distribution of the compound of the general formula [1], the presence of a polymer material is not essential,
A small amount (2
(% By mass or less) of a polymer material. Specific examples of the resin to be added include olefin polymers and copolymers (eg, polyethylene, polypropylene, polyisobutylene, ethylene-vinyl acetate copolymer, ethylene −
Acrylate copolymer, ethylene-methacrylate copolymer, ethylene-methacrylic acid copolymer, etc.), vinyl chloride copolymer (for example, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer), vinylidene chloride copolymer, Vinyl alkanoate polymers and copolymers, allyl alkanoate polymers and copolymers, polymers and copolymers of styrene and its derivatives (eg butadiene-styrene copolymer, isoprene-styrene copolymer, styrene-methacrylate) Copolymer, styrene-acrylate copolymer, etc.), acrylonitrile copolymer, methacrylonitrile copolymer, alkyl vinyl ether copolymer, acrylic ester polymer and copolymer, methacrylic ester polymer and copolymer , Itaconic acid diester polymers and copolymers, Water maleic acid copolymer, acrylamide copolymer, methacrylamide copolymer, phenol resin, alkyd resin, polycarbonate resin, ketone resin, polyester resin, silicone resin, amide resin, hydroxyl and carboxyl group-modified polyester resin, butyral resin, Polyvinyl acetal resin, urethane resin, rosin resin, hydrogenated rosin resin, petroleum resin, hydrogenated petroleum resin, maleic acid resin, terpene resin, hydrogenated terpene resin, chroman-indene resin, cyclized rubber-methacrylic acid ester copolymer Copolymer, a cyclized rubber-acrylate copolymer, a copolymer containing a nitrogen-free heterocyclic ring (for example, as a heterocyclic ring, a furan ring, a tetrahydrofuran ring, a thiophene ring, a dioxane ring, a dioxofuran ring, a lactone ring, Benzo Orchid ring, benzoin thiophene ring, 1,3-dioxetane ring), and epoxy resins.

When resin particles dispersed in the oil-based ink used in the present invention are added, the content is preferably 0.1 to 2% by mass of the whole ink. When the content is large, clogging of the ink in the discharge head is likely to occur, and it is difficult to obtain stable ink discharge.

The oil-based ink used in the present invention contains a coloring material as a coloring component together with the above-mentioned dispersed resin particles in order to make the non-image area light-opaque at the time of making the non-image area hydrophilic by light irradiation. Preferably. As the coloring material, any pigments and dyes conventionally used in oil-based ink compositions or liquid developers for electrostatography can be used.

As the pigment, those generally used in the technical field of printing can be used irrespective of inorganic pigments and organic pigments. Specifically, for example, carbon black, cadmium red, molybdenum red, chrome yellow, cadmium yellow, titanium yellow, chromium oxide, pyridian, titanium cobalt green, ultramarine blue, Prussian blue, cobalt blue, azo pigments, phthalocyanine-based Pigments, quinacridone pigments, isoindolinone pigments, dioxazine pigments, threne pigments, perylene pigments, perinone pigments, thioindigo pigments, quinophthalone pigments, metal complex pigments, and other conventionally known pigments are particularly limited. It can be used without.

As the dye, an azo dye, a metal complex dye,
Naphthol dye, anthraquinone dye, indigo dye,
Oil-soluble dyes such as carbonium dyes, quinone imine dyes, xanthene dyes, cyanine dyes, quinoline dyes, nitro dyes, nitroso dyes, benzoquinone dyes, naphthoquinone dyes, phthalocyanine dyes and metal phthalocyanine dyes are preferred. These pigments and dyes may be used alone or in an appropriate combination, but are desirably contained in the range of 0.01 to 5% by weight based on the whole ink.

These coloring materials may be dispersed in a non-aqueous solvent as the dispersed particles themselves or separately from the dispersed resin particles, or may be contained in the dispersed resin particles. In the case of containing, pigments and the like are generally coated with the resin material of the dispersed resin particles to form resin-coated particles. General. The average particle diameter of these particles including the resin particles dispersed in the non-aqueous solvent of the present invention, and also the colored particles, is preferably 0.10 μm to 1 μm. More preferably, it is 0.15 μm to 0.8 μm. This particle size is CA
It was obtained with a PA-500 particle size analyzer (trade name, manufactured by Horiba, Ltd.).

As the non-aqueous drawing ink used in the present invention, a method for producing a paint or a liquid developer for electrostatography can be used. For example, these methods are described in Kenji Ueki, “Flow of paint and pigment”. Dispersion, Kyoritsu Shuppan (1971)
Year), "Solomon, Science of Paint", "Paint and Surfac"
e Coating and Theory and Practice ", Yuji Harazaki" Coating Engineering "Asakura Shoten (1971), Yuji Harasaki" Basic Science of Coatings "Maki Shoten (1977), etc.

Specifically, for example, British Patent No. 8934
No. 29, No. 93038, U.S. Pat.
No. 3,900,412, No. 4,606,899, JP-A-60-179751, JP-A-60-185963,
It can be prepared according to the method described in JP-A-2-13965.

The charge control agent as described above is preferably used in an amount of 0.001 to 1.0 part by weight with respect to 1000 parts by weight of the carrier liquid. If desired, various additives may be added. The upper limit of the total amount of these additives is regulated by the electric resistance of the oil-based ink. That is, if the electrical resistance of the ink from which the dispersed particles have been removed is lower than 10 ⁹ Ω · cm, it becomes difficult to obtain a high-quality continuous tone image. is necessary.

Next, a method of forming an image on the lithographic printing plate precursor (hereinafter, also referred to as “master”) will be described. FIG. 1 shows an example of an apparatus system for performing such a method. The apparatus system shown in FIG. 1 has an ink jet recording apparatus 1 using oil-based ink.

As shown in FIG. 1, first, pattern information of an image (graphics or text) to be formed on the master 2 is transmitted from an information supply source such as a computer 3 through a transmission means such as a bus 4 to an oil-based ink. Is supplied to the ink jet recording apparatus 1 that uses. 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, sprays minute droplets of the ink on the master 2 according to the information. Thereby, the ink adheres to the master 2 in the pattern. Thus, an image is formed on the master 2 to obtain a plate-making master (plate-making printing original plate).

FIGS. 2 and 3 show examples of the configuration of an ink jet recording apparatus in the apparatus system shown in FIG. 2 and 3
In FIG. 2, members common to those in FIG. 1 are indicated using 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. Head 1 provided in ink jet recording apparatus
0 is the upper unit 10 as shown in FIGS.
1 and a slit sandwiched between the lower unit 102,
The tip is a discharge slit 10a, a discharge electrode 10b is arranged in the slit, and the oil ink 11 is filled in the slit.

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, a counter electrode 10c is provided so as to face the discharge electrode 10b.
A master 2 is provided above. By applying a voltage, a circuit is formed between the discharge electrode 10b and the counter electrode 10c, and the oily ink 11 is discharged from the discharge slit 10a of the head 10 to form an image on the master 2 provided on the counter electrode 10c. Is done.

The width of the discharge electrode 10b is preferably as narrow as possible to form a high quality image, for example, for printing. For example, the oil-based ink is used for the head 10 in FIG.
, Using the discharge electrode 10b having a tip of 20 μm width,
By setting the distance between the ejection electrode 10b and the counter electrode 10c to 1.5 mm and applying a voltage of 3 KV for 0.1 millisecond between the electrodes, a 40 μm dot print can be formed on the master 2.

The plate-making original plate obtained as described above may be irradiated with ultraviolet light at the entire stage at each stage to selectively convert only the non-image portions to a hydrophilic surface state. As a light source of the ultraviolet light, any lamp having a wavelength of 200 to 450 nm may be used. Preferably 250-3
One in which a wavelength of 30 nm is effectively used is mentioned.

[Printing] After forming an image distribution of lipophilicity and hydrophilicity on the surface of the printing original plate, it can be directly sent to an offset printing step without development processing. Therefore, it has many advantages, mainly simplicity, as compared with the known lithographic printing method. That is, as described above, the chemical treatment with the alkali developing solution is unnecessary, and the accompanying wiping and brushing operations are not required, and further, there is no environmental load due to the discharge of the developing waste solution. It is also an advantage that printing is easily performed from the simple image recording means as described above.

The non-image area of the lithographic printing plate is sufficiently hydrophilic, but if necessary, it may be washed with washing water, a rinsing solution containing a surfactant or the like, or a desensitizing solution containing gum arabic or a starch derivative. May be processed. As the post-processing when the image recording material of the present invention is used as a printing plate material, these processings can be used in various combinations. As the method, a method of applying the printing solution on a lithographic printing plate with a sponge or absorbent cotton impregnated with the surface conditioning solution, or immersing the printing plate in a vat filled with the surface conditioning solution, Application by an automatic coater is applied. Further, it is more preferable that the application amount is made uniform with a squeegee or a squeegee roller after the application. The application amount of the surface conditioning liquid is generally 0.03 to 0.8 g / m ² (dry weight)
Is appropriate. The lithographic printing plate obtained by such a process is set on an offset printing press or the like, or is made on a printing press, and used for printing a large number of sheets.

Next, the process of reproducing the printing plate after printing will be described. [Regeneration of printing plate] After printing, the printing plate is washed away with a hydrophobic petroleum solvent using a petroleum solvent. Examples of the solvent include aromatic hydrocarbons such as kerosene and isoper as commercially available printing ink dissolving liquids, and benzol, toluene, xylol, acetone, methyl ethyl ketone, kerosene, and a mixed solvent thereof may be used. If the image substance does not dissolve, gently wipe it with a cloth. In some cases, a 1/1 mixed solvent of toluene / Daiclean may be used.

The washed printing plate is then heated to a temperature equal to or higher than the thermal decomposition temperature of the compound of the general formula (1) forming a hydrophobic region on the surface of the printing plate, and this compound is thermally decomposed to obtain a hydrophobic material. The groups are released, the hydrophilic surface is restored, and the original printing plate having a uniform hydrophilic surface is regenerated. This thermal decomposition depends on the kind of the compound of the general formula (1),
Since it occurs more than 00 ° C and mostly at about 300 ° C,
Preferably, heating to 350 ° C. is good. If the printing plate material is a substance having photocatalytic ability, this temperature also corresponds to the high-temperature hydrophilicity developing temperature. In other words, many metal oxides having photocatalytic ability become hydrophobic when heated to a certain temperature level, and have the property of recovering a hydrophilic surface when heated to a high temperature (high-temperature hydrophilicity development temperature). In the invention, it is considered that this property also contributes to the reproduction of the printing original plate.

The regenerating operation of the printing plate from which the ink has been washed and removed by the above method can be performed at any time between the time when the printing ink is washed and removed and the time when imagewise irradiation with actinic light is performed in the next plate making operation. Good.

Although the number of reproducible reproductions of the printing plate according to the present invention has not been completely grasped, it is at least 15 times or more. It is considered that it is restricted by mechanical deformation (strain) of the plate material.

[Aspects of Apparatus] The constituent materials of the printing original plate and the plate making operation in the present invention have been described. Next, a method and an apparatus for performing printing by mounting the original plate will be described with reference to the drawings. The printing plate having a heat-responsive substance having photocatalytic ability on its surface may be fixed as a component of the plate cylinder, or may be detachable. In the following description of FIG. 4 and the following, an example in which the simplicity of the present invention is remarkably exhibited, that is, an example in which a printing plate is fixed on a plate cylinder will be described.

FIG. 4 is a diagram showing the configuration of an offset printing apparatus according to an example of the first embodiment of the present invention. As shown in FIG. 4, an offset printing apparatus according to an embodiment of the present invention includes a plate cylinder 41 having a surface having the above-described photocatalytic substance such as titanium oxide or zinc oxide on its surface, and an actinic light for the plate cylinder 41. The compound of the general formula (1) according to the present invention is applied to the plate cylinder 41, which has been subjected to irradiation to make the entire surface of the original plate hydrophilic, and the plate cylinder 41, which has been made completely hydrophilic, using an inkjet apparatus. Drawing unit 45 for forming a hydrophilic / hydrophobic image-like distribution by performing drawing with ink to be printed, ink / fountain solution supply unit 43 for supplying ink and fountain solution to plate cylinder 41, and printing end Later plate cylinder 41
And an ink washing unit 44 for removing the ink remaining in the ink, and heating the washed plate to the thermal decomposition temperature of the compound of the general formula [1] (sometimes called the high-temperature hydrophilicity-expressing temperature because its action and temperature are almost the same). A heating unit 49, a blanket 46 as an intermediate for transferring the ink held on the plate cylinder 41 to the sheet, and an impression cylinder 47 for holding the sheet fed together with the blanket 46 are provided. It is housed in the main body 48. Both the heating unit 49 and the hydrophilic treatment unit 42 may be provided, or only one of them may be provided.

In the present embodiment, a mercury lamp is used as a light source for the hydrophilicity treatment section 42, but another light source containing an ultraviolet component such as a xenon discharge lamp or a high-intensity halogen / tungsten lamp may be used. With the slits arranged in a direction perpendicular to the rotation direction of the plate cylinder, the entire surface of the plate cylinder is exposed to the scanning light by the slit light with the rotation of the plate cylinder. The width of the slit need not necessarily be narrow as in the case of drawing by light. Further, as described above, scanning exposure with laser light that does not narrow the beam diameter may be used. Subsequently, ink-jet drawing is performed while passing through the ink-jet drawing section 45 or while the rotation of the plate cylinder is stopped, so that an image-like hydrophilic / hydrophobic distribution is formed on the surface of the original plate. In the former case, the ink ejection speed and the rotation speed of the plate cylinder are determined so that drawing is performed appropriately. After inkjet drawing,
In order to promptly dry and remove the solvent, a dryer for heating or air drying may be provided. A temperature of 100 ° C. or less is sufficient.

The ink jet drawing unit 45 discharges ink droplets in accordance with an electric signal carrying image information to form a hydrophobic area on the plate surface. FIG. 5 is a configuration example of the drawing unit 45 using the inkjet apparatus. Editing / Layout W /
In step S60, the driving unit 59 of the inkjet apparatus modulates the electric signal into a droplet discharge signal based on the image signal S which is converted into a signal from the image to be printed and is input to the recording unit. Is ejected toward, and drawing is performed on the surface of the plate cylinder 1.

Next, the operation of the first embodiment will be described together with the case where the imagewise hydrophilic region is formed in the active light irradiating section 5 and the case where it is formed in the high temperature heating section 5. First, the surface portion of the plate cylinder 41 that passes while rotating the hydrophilicity-treating section 42 that irradiates active light to make the entire surface hydrophilic becomes hydrophilic. The plate cylinder whose entire surface has been rendered hydrophilic is provided with an image-like distribution of hydrophobic droplets by the ejection of droplets modulated with image information in an ink-jet type drawing unit 45, and a hydrophilic / lipophilic image is formed. A distribution is obtained. When the ink-jet drawing is completed, the ink and dampening solution are supplied to the plate cylinder 41 from the ink / fountain solution supply unit 43. Thereby, the plate cylinder 4
In one lipophilic image area, the ink is held, and in the hydrophilic non-image area, the fountain solution is held without holding the ink.

Thereafter, a sheet is supplied between the blanket 46 and the impression cylinder 47 as shown by an arrow A, and the ink held in the plate cylinder 1 is transferred to the sheet via the blanket 46 to perform offset printing. Is

After the printing is completed, the ink remaining on the plate cylinder 41 is removed by the ink washing unit 44, and the plate, whose ink has been washed by the heating unit 49, is heated to the thermal decomposition temperature of the compound of the general formula [1]. After forming the surface, and subsequently or after storage, it is used again as a printing plate. Even in the case of storage, by making the reproduction original plate hydrophilic through the affinity processing unit 42, even if the plate cylinder 41 is touched with a hydrophobic atmosphere during storage, such a history is erased and uniform. The hydrophilic surface is secured.

As described above, according to the offset printing apparatus of the present invention, the plate cylinder 1 is formed only by the formation of a uniform surface which is entirely hydrophilic by irradiation with actinic light and the imagewise distribution of the compound of the general formula [1] by the ink jet method. Thus, it is possible to perform offset printing that does not require development and maintains the sharpness of the printing surface. Further, since the plate cylinder 41 can be returned to the original state by washing the plate cylinder 41 and subjecting the plate to a heat treatment at a temperature equal to or higher than the thermal decomposition temperature of the compound represented by the general formula (1), the plate cylinder 41 is repeatedly used. As a result, the printed matter can be provided at low cost. Further, since there is no need to remove the plate cylinder 41 from the printing apparatus, dust and the like do not adhere when the printing apparatus is incorporated into the printing apparatus as in the conventional PS plate, and thereby the printing quality can be improved.

Further, a plate cylinder 41 is used as a printing original plate, and a hydrophilic treatment section 42, an ink / fountain solution supply section 43, an ink washing section 44, a drawing section 45, and a heating / reproducing section are provided around the plate cylinder 41. 49, the plate cylinder 1
By simply rotating, the entire surface of the original plate can be made hydrophobic, imagewise irradiation with actinic light, ink and dampening water can be supplied, and ink washing after printing is completed. Thus, space can be saved.

[0110]

[Example 1] An example according to the first embodiment will be described. Rolled 0.30 mm thick JISA1050 aluminum material containing 0.01 wt% of copper, 0.03 wt% of titanium, 0.3 wt% of iron, and 0.1 wt% of silicon in 99.5 wt% aluminum The plate was grained using a 20% by weight aqueous suspension of pumicestone (manufactured by Kyoritsu Ceramics Co., Ltd.) of 400 mesh and a rotating nylon brush (6,10-nylon), and then thoroughly washed with water. This one
5% by weight sodium hydroxide aqueous solution (aluminum 4.5
Weight%) and the amount of aluminum dissolved is 5 g / m ²
And then washed with running water. Further, it is neutralized with 1% by weight nitric acid, and then, in a 0.7% by weight nitric acid aqueous solution (containing 0.5% by weight of aluminum), a rectangular wave having a voltage of 10.5 volts at the anode and a voltage of 9.3 volts at the cathode. Alternating waveform voltage (current ratio r = 0.90, Japanese Patent Publication No. 58-5796)
Using the current waveform described in the embodiment of
Electrolytic surface-roughening treatment was carried out at an anode charge of 0 clones / dm ² . After washing with water, it was immersed in a 10% by weight aqueous solution of sodium hydroxide at 35 ° C., etched so that the amount of aluminum dissolved was 1 g / m ² , and then washed with water. Next, at 50 ° C, 3
After immersing in 0% by weight sulfuric acid aqueous solution and desmutting,
Washed with water.

Further, a porous anodic oxide film forming treatment was carried out in a 20% by weight aqueous sulfuric acid solution (containing 0.8% by weight of aluminum) at 35 ° C. using a direct current. That is, electrolysis was performed at a current density of 13 A / dm ² , and the anodic oxide film weight was adjusted to 2.7 g / m ² by adjusting the electrolysis time. After washing this support with water,
It was immersed in a 3% by weight aqueous solution of sodium silicate at 70 ° C. for 30 seconds, washed with water and dried. The aluminum support obtained as described above had a reflection density of 0.30 and a center line average roughness of 0.58 μm as measured by a Macbeth RD920 reflection densitometer.

Next, this aluminum support was placed in a vacuum evaporation apparatus, and a partial pressure of 7 was adjusted so that the total pressure became 0.02 Pa.
The titanium metal piece was electroheated under the condition of 0% oxygen gas and deposited on an aluminum support to form a titanium oxide thin film. The crystal component of this thin film has an amorphous / anatase / rutile crystal structure ratio of 1.5 / 6.
5/2, and the thickness of the TiO ₂ thin film was 90 nm. This was wound around the substrate of the plate cylinder 1 to obtain an original plate for on-press printing.

Next, in the hydrophilic processing section 42 shown in FIG. 4, slit light irradiation of active light was performed while rotating the plate cylinder to make the entire surface of the original plate hydrophilic. The activation light is US10
Light source device UNIREC URM600 type GH60201X
Light intensity of 100 mW using (Ushio Electric Industry Co., Ltd.)
The plate cylinder was rotated at a rotation speed at which the transit time was 15 seconds under / cm ² . Contact angle meter CA-D (manufactured by Kyowa Interface Science Co., Ltd.)
When the contact angle of the surface with water was measured by the aerial water droplet method using the method, each irradiation area was between 3 and 6 degrees.

Next, n was added to toluene at a concentration of 0.1% by mass.
-A drawing solution in which octadecyltrichlorosilane is dissolved is filled in an ink jet ink cassette, and the ink is used as an ink to draw on the surface of the original plate from an ink jet device attached to the ink jet drawing unit 45 in FIG. An image-like ink (hydrophobic) area was formed. Contac is the contact angle of the hydrophobic area
t Angle Meter CA-D (manufactured by Kyowa Interface Science Co., Ltd.) was measured by the air droplet method.
It was between 1 degree and was sufficiently hydrophobic.

The plate cylinder 1 is used in a single-sided printing machine of Oliver 52 manufactured by Sakurai Co., Ltd., and the dampening water is supplied to the ink / fountain solution supply unit 3 by pure water and the ink is supplied by Newc manufactured by Dainippon Ink and Chemicals, Inc.
3,000 sheets were printed using hampion F gloss 85 ink. A clear printed matter was obtained from the start to the end, and no damage to the plate cylinder 1 was observed.

Next, in the washing unit 4, the surface of the plate cylinder 1 is thoroughly washed by soaking a 1/1 mixed solution of printing ink washing liquid Daiclean R (released by Dainippon Ink and Chemicals, Inc.) and toluene into a waste cloth. To remove the ink. Next, the plate cylinder is rotated at a slow rotational speed so that the residence time in the heating unit is 2 minutes while performing electroheating so that the plate surface becomes 350 ° C. in the heating / reproducing unit 49, and then the plate surface is cooled with cold air. After cooling, the contact angle was measured in the same manner as before. Every part of the plate surface was between 3 and 6 degrees.

Next, after the entire surface of the plate cylinder 1 was uniformly exposed to light under the same conditions as above to ensure the hydrophilicity, drawing by ink jet was repeated under the same conditions as above. The plate cylinder 1 is used for a single-sided printing machine of Oliver 52 manufactured by Sakurai Co., Ltd., and the dampening water is supplied to the ink / fountain solution supply unit 3 by pure water and the ink is supplied by Newchamp by Dainippon Ink and Chemicals, Inc.
Offset printing was performed on 5000 sheets using ion F gloss 85 ink. A clear printed matter was obtained from the start to the end, and no damage to the plate cylinder 1 was observed.

When the above repetition was performed 5 times, no change was observed in the value of the contact angle after irradiation with the active light, the speed of recovery of the contact angle by heating, and the sharpness of the image on the printed surface. From these results, using a printing original plate having a titanium oxide layer provided on an aluminum support, using the printing apparatus of Embodiment 1, uniform irradiation of active light, formation of a hydrophobic image area of an inkjet system, and post-printing It was shown that plate making printing and repeated reuse of the original plate were possible by removing the ink and heating to the high hydrophilicity developing temperature.

Example 2 A SUS plate having a thickness of 100 μm was set in a vacuum deposition apparatus, and zinc selenide was deposited to a thickness of 100 nm under a vacuum of a total pressure of 0.65 Pa. This was oxidized in air at 600 ° C. for 2 hours to form a zinc oxide thin film on one surface of the SUS plate. This 100-micron SUS plate with a zinc oxide film was wound around the substrate of the plate cylinder 1 of the printing apparatus of the first embodiment in the same manner as in the first embodiment to obtain an on-press plate-making type original plate.

Next, the same Unilec URM as in the first embodiment is used.
Under the same conditions using a 600 type GH60201X, the surface of the original plate was uniformly irradiated with active light. When the contact angle of water on the surface of the original plate after irradiation was measured by a water drop method in the air using Contact Angle Meter CA-D, the contact angle of water on all surfaces was between 10 and 13 degrees.

Using the ink jet apparatus of the embodiment shown in FIGS. An image-like distribution of a hydrophobic surface was formed on the surface of the original plate. Contact angle meter CA-D (manufactured by Kyowa Interface Science Co., Ltd.)
When measured by the aerial water droplet method using the method, each part was between 90 and 95 degrees.

The plate cylinder 1 was used for a single-sided printing machine of Oliver 52 manufactured by Sakurai Co., Ltd., and the dampening water was supplied to the ink / fountain solution supply unit 3 by pure water and the ink was supplied by Dainippon Ink and Chemicals, Newc.
Offset printing was performed on 1,000 sheets using hampion F gloss 85 ink. A clear printed matter was obtained from the start to the end, and no damage to the plate cylinder 1 was observed.

Next, in the washing section 44, the surface of the plate cylinder 1 is thoroughly washed by soaking a 1/1 mixture of the printing ink washing liquid Daiclean R (released by Dainippon Ink and Chemicals) and toluene into a waste cloth. Then, the ink was removed and heated to 350 ° C. by the heating unit 49. The entire surface of the original plate was irradiated with actinic light using a Unirec URM600 format GH60201X. The contact angle of water on the original plate surface after irradiation
When the contact angle of the surface with water was measured by the air droplet method using the ntact Angle Meter CA-D, each irradiation area was between 10 and 13 degrees. An image-like distribution of a hydrophobic surface was formed on the surface of the original plate which had been subjected to a hydrophilic treatment using the same ink jet apparatus and drawing solution as the first time on the plate cylinder.

The plate cylinder 1 is used in a single-sided printing press of Oliver 52 manufactured by Sakurai Co., Ltd., and the dampening water is supplied to the ink / fountain solution supply unit 3 by pure water and the ink is supplied by Newc manufactured by Dainippon Ink and Chemicals, Inc.
Offset printing was performed on 1,000 sheets using hampion F gloss 85 ink. A clear printed matter was obtained from the start to the end, and no damage to the plate cylinder 1 was observed.

From these results, using a printing original plate having a zinc oxide layer provided on a SUS support, the entire surface was irradiated with actinic light using the printing apparatus of Embodiment 1 and an image layer was formed with the compound of the general formula (1). It was shown that printing was possible, and that the printing original plate could be repeatedly reused only by washing and removing the ink and heating and regenerating.

[Example 3] An aluminum support anodized in the same manner as in Example 1 was replaced with CsLa ₂ NbTi ₂
The surface was hydrolyzed by immersion in a 20% ethanol solution containing cesium ethoxide, titanium butoxide, lanthanum isobutoxide, and niobium ethoxide corresponding to the stoichiometric ratio of O ₁₀ , and then heated to 280 ° C. to support aluminum. A thin film of CsLa ₂ NbTi ₂ O _{10 having} a thickness of 1000 Å was formed on the body surface.

Except that this aluminum support with a composite metal oxide thin film was wound around the base of a plate cylinder to form an original plate, plate making, printing and ink washing and removal were carried out in the same manner as in Example 1, and represented by the general formula (1). The plate was heated and regenerated and reprinted at a temperature equal to or higher than the thermal decomposition temperature of the compound. However, in this case, the heating temperature was 380 ° C., the rotation speed of the plate cylinder was increased, and the residence time of the heating section was 60 seconds. The contact angle of water in the hydrophobic region where the n-octadecyltrichlorosilane layer is formed is 85 to 90 degrees in each of the first and second times.
The contact angle of the active light irradiation area was 9 to 12 degrees. The quality of the printed surface was not stained in the first and second runs, and the discriminability between the image area and the non-image area was sufficient.

Example 4 A polyimide (pyromellitic anhydride / m-phenylenediamine copolymer) film (trade name; Kapton, manufactured by Dupont Toray) having a thickness of 100 μm was set in a vacuum evaporation apparatus, A master plate using titanium as a thermoresponsive metal oxide was prepared. That is, the polyimide support was set in a sputtering apparatus, and a titanium metal piece was heated under the conditions of a total pressure of 0.02 Pa and an oxygen partial pressure of 70% to deposit a titanium dioxide thin film by vapor deposition.
According to the X-ray analysis method, the crystal component of this thin film is amorphous,
The structure ratio of each crystal of anatase and rutile is 15 / 6.5 /
It was 2. The heat of the titanium dioxide thin film is 90 nm.
Met. The same plate making, printing and ink as in Example 1 except that this was wound around the substrate of the plate cylinder and used as an original plate, and a 75 W low-pressure xenon discharge lamp was used as a light source for the active light at a light intensity of 1200 mW / cm 2. Washing removal and thermal decomposition were performed. Next, the entire surface was irradiated again from a 75 W low-pressure xenon discharge lamp, and plate making and printing were performed again as in the example. The contact angle of the hydrophobic region with water is 69 to 72 degrees for the first and second times, and
The contact angle of the active light irradiation area was 10 to 15 degrees.
The quality of the printed surface was not stained in the first and second runs, and the discriminability between the image area and the non-image area was sufficient.

Example 5 The same process as in Example 1 was carried out except that the solution for forming the hydrophobic image area was a xylene solution containing 0.5% of hexadecyldimethylchlorosilane and 0.02% of cyclohexanol. Printing and original plate reproduction were performed. The contact angle with water in the hydrophobic region where the hexadecyldimethylchlorosilane layer was formed was 73 to 75 degrees in both the first and second times, and the contact angle in the active light irradiation region was 8 to 11 degrees. Was. Printing surface quality is also 1
There was no background stain in the first and second runs, and the discrimination between the image area and the non-image area was sufficient.

Example 6 A solution for forming a hydrophobic image area was prepared by adding 0.5% of n-octadecyldimethylchlorotitanium to
Except that the xylene solution was 0.02% cyclohexanol, the same operations as in Example 1 were performed to make a plate, print, and regenerate an original plate. The contact angle of water in the hydrophobic region where the n-octadecyldimethylchlorotitanium layer is formed is 70 to 72 degrees for the first and second times, and the contact angle of the active light irradiation region is 10 to 13 degrees. Met. The quality of the printed surface was not stained in the first and second runs, and the discriminability between the image area and the non-image area was sufficient.

Example 7 The solution for forming a hydrophobic image area used in Example 6 was prepared by adding 0.5% of n-octadecyldimethylchlorotitanium and carbon black (average diameter 35 nm).
Except that the xylene solution was 0.02% and octyl alcohol was 0.02%, the same operation as in Example 6 was performed to make a plate,
Printing and original plate reproduction were performed. The results were the same as in Example 6.

[0132]

The hydrophilic surface of the present invention, in particular, the hydrophilic surface having photocatalytic activity, is drawn by an ink jet method using a hydrophobic solution containing the compound of the general formula (1) to form a hydrophobic image-like region. The printing method of forming and printing is a plate making method that does not require a development process and is simple in operation, and can obtain a clear print image quality free from printing stains. It is also possible to make a plate on a press, and if a material having photocatalytic properties is used, remove the ink from the printed plate and use the general formula
By subjecting the plate to a heat treatment at a temperature equal to or higher than the thermal decomposition temperature of the compound represented by (1), the used plate can be reproduced on a printing plate.

[Brief description of the drawings]

FIG. 1 is a schematic configuration diagram showing an example of an apparatus system used in the present invention.

FIG. 2 is a schematic configuration diagram illustrating a main part of an inkjet recording apparatus used in the present invention.

FIG. 3 is a partial sectional view of a head of an ink jet recording apparatus used in the present invention.

FIG. 4 is a schematic diagram illustrating a configuration of an offset printing apparatus according to a first embodiment of the present invention.

FIG. 5 is a schematic diagram illustrating a configuration of a hydrophobic processing section related to rendering of a hydrophobic image by an inkjet method.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Ink jet recording apparatus 2 Master 3 Computer 4 Bus 10 Head 10a Discharge slit 10c Counter electrode 11 Oil ink 101 Upper unit 102 Lower unit 41 Plate cylinder 42 Hydrophilization processing part 43 Ink / fountain solution supply part 44 Ink cleaning part 45 Ink jet Drawing unit 46 Blanket 47 Impression cylinder 48 Main body 49 Heat reproduction unit 57 Inkjet device 58 Droplet discharge nozzle 59 Modulation / drive unit 60 Editing / layout W / S

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) B41M 1/06 B41N 1/14 2H114 B41N 1/08 B41F 31/02 A 1/14 B41J 3/04 101Z F Terms (Reference) 2C034 AA12 BA02 2C056 FB01 FB08 2C250 DB01 FA03 FB12 2H084 AA25 AE05 BB02 BB16 CC05 2H113 AA01 AA05 BA05 DA04 DA07 DA64 EA02 FA07 FA29 2H114 AA04 AA22 BA10 DA04 GA03 EA03 GA03 GA03 EA08

Claims (8)

[Claims] 1. A hydrophobic image formed by image-wise drawing a solution containing at least a compound represented by the following general formula (1) as an ink on a surface of an offset printing plate having a hydrophilic surface by an ink jet method. An offset printing method, wherein an area is formed, and the image area is brought into contact with a printing ink to form a printing surface in which the area has received the ink, and printing is performed. G _n JM _4-n (1) (wherein G represents a hydrophobic organic group, and J represents C, Si, G
e represents an element having a valence of 4, selected from Ti, Zr and Sn, M represents a halogen or an alkoxy group, and n represents 1
Represents an integer of 1 to 3. ) 2. The offset printing plate having a hydrophilic surface is an offset printing plate whose surface has been made hydrophilic by irradiating actinic light to the printing plate having photocatalytic activity. The offset printing method described. 3. A printing plate which has been subjected to a heat treatment at a temperature not lower than the thermal decomposition temperature of the compound represented by the general formula (1) after washing and removing the ink remaining on the plate surface of the printing plate used for printing. 3. The printing method according to claim 1 or 2, wherein printing is performed by repeating the operation according to claim 1 or 2 as a printing original plate. 4. The surface of a printing original plate is made of TiO ₂ , RTi
O ₃ (R is an alkaline earth metal atom), AB _2-x C _x D
_{3-x E x O 10 (} A is a hydrogen atom or an alkali metal atom, B is an alkaline earth metal atom or a lead atom, C is a rare earth atom, D is a metal atom belonging to Group 5A elements of the periodic table, E
Is a metal atom belonging to the 4A group element, and x represents an arbitrary numerical value of 0 to 2), SnO ₂ , Bi ₂ O ₃ , ZnO, Z
4. The device according to claim 1, comprising at least one metal oxide selected from rO, GeO _2, and FeO _y (y = 1.0 to 1.5). 5. Offset printing method. 5. An offset printing apparatus used in the method according to claim 1, wherein a printing plate having a photocatalytic ability is mounted, and the printing plate is activated light. Irradiating means for rendering the surface hydrophilic by irradiating; drawing means for performing ink jet drawing on the original plate to form a hydrophobic image area; supplying printing ink to the image area so that the image area becomes ink 1. An offset printing apparatus, comprising: an ink supply unit for forming a printing surface that has received the print data; and a printing unit for performing printing by bringing the printing surface into contact with the surface to be printed. 6. An ink washing means for removing ink remaining on the printing plate after printing is completed, and a heating means for heating the washed printing plate surface to a temperature higher than the thermal decomposition temperature of the compound of the general formula (1). The offset printing apparatus according to claim 5, wherein 7. The printing apparatus according to claim 5, wherein at least the exposing means, the drawing means, the ink supply means, the ink removing means, and the plate surface heating means are arranged around the plate cylinder.
An offset printing device according to claim 1. 8. A printing plate comprises a part of a plate cylinder, wherein at least an exposing means, a drawing means, an ink supply means and an ink removing means are arranged around the plate cylinder. The offset printing apparatus according to any one of claims 5 to 7, wherein