JP2001305725A - Direct pattern forming original plate of waterless planographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a direct pattern forming original plate of a waterless planographic printing plate developable with water only. SOLUTION: The direct pattern forming original plate of a waterless planographic printing plate has at least a heat sensitive layer and a silicone rubber layer in this order on a substrate and the contact angle of water to the silicone rubber layer is <=110 deg..

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a direct drawing type waterless lithographic printing plate precursor which can be directly made by a laser beam, particularly without any treatment using an organic solvent.
The present invention relates to a direct drawing type waterless planographic printing plate precursor that can be developed only with a liquid containing water as a main component.

[0002]

2. Description of the Related Art A so-called direct drawing type plate making, in which an offset printing plate is produced directly from an original without using a plate making film, is simple, which does not require skill, rapidity in which a printing plate can be obtained in a short time, Taking advantage of features such as rationality that can be selected from various systems according to quality and cost, the company has begun to enter not only the light printing industry but also the fields of general offset printing and flexographic printing. In particular, a new type of various direct-drawing lithographic printing plates has recently been developed with the rapid progress of output systems such as a prepress system, an image setter, and a laser printer. These direct-drawing lithographic printing plates can be classified according to plate-making methods, such as a method of irradiating a laser beam, a method of writing with a thermal head, a method of partially applying a voltage with a pin electrode, an ink repellent layer or an ink-coated layer by inkjet. And the like. Above all, the method using laser light is resolution,
It is superior to other methods in terms of plate making speed and there are many types.

[0003] The printing plate using the laser light further includes:
There are two types: a photon mode by photoreaction and a heat mode in which photothermal conversion is performed to cause a thermal reaction. In particular, the heat mode method has the advantage that it can be handled in a bright room, and due to the rapid progress of the semiconductor laser as a light source, it has recently attracted much attention,
It is said that it will become the mainstream in the future.

As a lithographic printing plate in the heat mode, a direct drawing type waterless lithographic plate capable of printing without using a dampening solution,
A PS plate with direct drawing water for printing using dampening water has been developed. The direct-drawing waterless lithographic printing plate has the advantages of obtaining high-quality printed matter and having a fast start-up of printing.
Since the system can be developed by a system of pretreatment with an organic solvent and brush rub development in the presence of water, there is an advantage that no alkali development waste liquid is generated when the PS plate is processed.

Although this pretreatment / water developing system is a very excellent system in practical use, development of a developing system using no organic solvent has been desired in view of further improvement in environmental awareness in recent years. It has become.

[0006]

SUMMARY OF THE INVENTION The object of the present invention is a technique which cannot be attained by the prior art, that is, a direct drawing type water which can be developed using only a liquid containing water as a main component without using any organic solvent. None The planographic printing plate precursor is provided.

[0007]

The direct drawing type waterless lithographic printing plate precursor according to the present invention is mainly characterized in order to solve the above problems. That is, "a direct drawing type waterless planographic printing plate precursor having at least a heat-sensitive layer and a silicone rubber layer in this order on a substrate, wherein a contact angle of water with respect to the silicone rubber layer is 110 ° or less. Lithographic printing plate precursor without water ".

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.

The direct-drawing waterless planographic printing plate precursor of the present invention comprises:
A direct-drawing waterless planographic printing plate precursor having at least a heat-sensitive layer and a silicone rubber layer in this order on a substrate, characterized in that the contact angle of water with the silicone rubber layer is 110 ° or less.

[0010] The contact angle of water to the silicone rubber layer is 1
By setting the angle to 10 ° or less, the wettability of the silicone rubber layer with respect to a liquid containing water as a main component during development can be maintained, and the developability with a liquid containing water as a main component can be improved.

The contact angle includes an advancing contact angle measured in a state where a liquid is wet and spread on a solid, and a receding contact angle measured in a state where a solid surface appears from the liquid. In the case of the present invention, when a liquid containing water as a main component is supplied to the printing plate surface during development, it is important how effectively the printing plate surface is wetted and developed. It is preferable to discuss in. Also, as a method of measuring the contact angle,
A droplet method, a tilt method, a vertical plate method, a powder method and the like can be mentioned, and the droplet method is known as the simplest method. This method uses a micro-injector on a flat plate sample and measures about 3 mm in diameter.
The following droplets are dropped, and the angle of the interface between the droplet and the flat plate sample after a certain time is measured by a reading microscope equipped with a goniometer.

As a method for obtaining such a silicone rubber layer, there are a method of laminating a film made of a polar material on the silicone rubber layer, a method of treating the surface of the silicone rubber layer, and a method of containing a hydrophilic component in the silicone rubber layer. And the like.

Preferred film materials used for lamination include polyethylene terephthalate, polyvinylidene chloride, polyvinyl alcohol, polyvinyl chloride and the like. Furthermore, even if the material of the film itself does not have polarity, a film coated with a hydrophilic substance or the like or a film subjected to a surface treatment is preferably used.

The surface treatment of the silicone rubber layer includes a plasma treatment and a corona treatment.

The hydrophilic component contained in the silicone rubber layer includes a hydrophilic silicone oil, a hydrophilic monomer /
Oligomers, epoxy compounds, glucose, fructose, sugars such as starch, cellulose derivatives such as methylcellulose, ethylcellulose, carboxymethylcellulose, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol,
Glycols such as tripropylene glycol and polypropylene glycol and monoalkyl ethers of these glycols, such as water-soluble polyurethane resins, water-soluble amide resins, hydrophilic polyacrylates and copolymers,
Examples include, but are not limited to, polyvinyl alcohol and its derivatives, surfactants, and the like.

Of these, hydrophilic silicone oils, hydrophilic monomers / oligomers, ethylene glycol derivatives, surfactants and the like are preferred.

Examples of the hydrophilic silicone oil include alkyl-modified silicone oil, polyether-modified silicone oil, alcohol-modified silicone oil, amino-modified silicone oil, epoxy-modified silicone oil, epoxy polyether-modified silicone oil, carboxy-modified silicone oil, and mercapto-modified silicone oil. Modified silicone oils in which various organic groups such as hydroxyl group, amino group, carboxyl group, sulfonic acid group, amide group, ethylene oxide group, etc. are introduced into a part of the methyl group in the molecule of silicone oil, amide modified silicone oil, etc. No.

Examples of the hydrophilic monomer / oligomer include monomers / oligomers having a functional group such as a hydroxyl group, an amino group, a carboxyl group, a sulfonic acid group and an amide group. Specific examples include dimethylaminomethyl (meth) acrylate, diethylaminomethyl (meth) acrylate, (meth) acrylic acid, itaconic acid, maleic acid, crotonic acid, sodium (meth) acrylate, ammonium (meth) acrylate, and styrene. Sulfonic acid,
Vinylsulfonic acid, acryloyloxymethylsulfonic acid, acrylamide, methylacrylamide, allyl alcohol, 2-hydroxyethyl acrylate,
-Hydroxypropyl (meth) acrylate, vinylpyridine and the like.

Examples of the ethylene glycol derivatives include diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, polyoxypropylene glycol (Mw: 200), and polyoxypropylene glycol monobutyl ether (Mw:
1200), tetraethylene glycol mono-2-ethylhexyl ether, diethylene glycol mono-2-
Ethylhexyl ether and the like.

Examples of the surfactant include polyoxyethylene alkyl allyl ethers, polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, polyoxyethylene alkyl amines, sorbitan esters, glycerin fatty acid esters, decaglycerin fatty acid. Nonionic surfactants such as esters, propylene glycol fatty acid esters, and pentaerythritol fatty acid esters; anionic surfactants such as sulfonates, sulfates, and phosphates;
Examples thereof include cationic surfactants such as quaternary ammonium salts and imidazolines, and amphoteric surfactants such as betaines and lecithins. Nonionic surfactants are preferred.

Specific examples of the nonionic surfactant include:
Polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene laurate , Polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, poly Oxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate,
Perfluoroalkyl polyoxyethylene ethanol,
Glyceryl monostearate, decaglyceryl monostearate, diglyceryl monooleate, pentaerythritol stearate and the like can be mentioned.

The content of the hydrophilic component used in the present invention may be within a range where the contact angle of water with respect to the silicone rubber layer is 110 ° or less. % By weight, more preferably 0.5 to 10% by weight. If the addition amount is 0.1% by weight or more, the effect of the addition is sufficiently exhibited, while the addition amount is 2%.
When the content is 0% by weight or less, the curability of the silicone rubber layer is not adversely affected, and the ink repellency is not adversely affected.

As the silicone rubber layer of the direct-drawing waterless planographic printing plate precursor according to the invention, any of an addition polymerization type and a condensation polymerization type can be used.

The components constituting the addition polymerization type silicone rubber layer include vinyl group-containing polydimethylsiloxane,
It contains a SiH group-containing polysiloxane, a reaction inhibitor for the purpose of controlling the curing rate, and a curing catalyst.

The vinyl group-containing polydimethylsiloxane is
It has a vinyl group at the molecular end and / or in the main chain. As the molecular weight, those having a molecular weight of several thousand to several hundred thousand can be used, but from the viewpoints of handleability, ink repellency and scratch resistance of the obtained printing plate, a weight average molecular weight of 10,000 to 20 is preferred.
It is preferable to use those having a size of 30,000 to 150,000.

Examples of the SiH group-containing polysiloxane include compounds having a SiH group in a molecular chain or at a terminal.

S in SiH group-containing polysiloxane
The amount of iH groups is preferably 2 or more, more preferably 3 or more in one molecule. The addition amount of the SiH group-containing polysiloxane is from 3 to 3 parts of the total composition of the silicone rubber layer.
It is preferably 20% by weight, more preferably 5 to 15% by weight. Speaking of the quantitative ratio with polydimethylsiloxane, the molar ratio of SiH group / vinyl group of polydimethylsiloxane is preferably 1.5 to 30,
10-20 are more preferred. When the molar ratio is 1.5 or more, the curing of the silicone rubber layer does not become insufficient, and when the molar ratio is 30 or less, the physical properties of the rubber become brittle and the scratch resistance of the printing plate is not adversely affected.

Examples of the reaction inhibitor include a nitrogen-containing compound, a phosphorus compound, and an unsaturated alcohol, and an alcohol containing an acetylene group is preferably used.
The preferable addition amount of the reaction inhibitor is 0.01 to 10% by weight in the silicone rubber composition, more preferably 1 to 10% by weight.
~ 5% by weight.

The curing catalyst is a Group III transition metal compound, preferably a platinum compound. Specifically, platinum alone, platinum chloride, chloroplatinic acid, olefin-coordinated platinum, an alcohol-modified complex of platinum, and platinum methyl A vinyl polysiloxane complex can be given as an example. The amount of such a curing catalyst is 0.01 to 20% by weight, preferably 0.1 to 10% by weight as a solid content in the silicone rubber layer. When the amount of the catalyst to be added is 0.01% by weight or more, the curing of the silicone rubber layer becomes sufficient, and there is no problem in the adhesion to the heat-sensitive layer. On the other hand, when the content is 20% by weight or less, the pot life of the silicone rubber layer solution is not adversely affected. In terms of the amount of metal such as platinum in the silicone rubber layer composition, 10 to 10
It is preferably 00 ppm, preferably 100 to 500 ppm.

In addition to these compositions, a silane or siloxane containing a hydrolyzable functional group, a known silane coupling agent, a titanate coupling agent, an aluminum coupling agent, etc. for the purpose of improving adhesiveness may be used. May be contained. As the silane coupling agent, alkoxysilanes, acetoxysilanes, ketoximine silanes and the like are preferable, and those having a vinyl group and ketoximine silanes are particularly preferable.

The components constituting the condensation-polymerized silicone rubber layer include a hydroxyl group-containing polydimethylsiloxane, a crosslinking agent (deacetic acid type, deoxime type, dealcohol type, deamine type, deacetone type, deamide type, Deaminoxy type), and a curing catalyst.

The hydroxyl group of the hydroxyl group-containing polydimethylsiloxane can be located at the molecular terminal and / or in the main chain, but those preferably used have a hydroxyl group at the molecular weight terminal. A molecular weight of several thousand to several hundred thousand can be used, but from the viewpoints of handleability, ink repellency and scratch resistance of the obtained printing plate, the weight average molecular weight is 1
It is preferable to use a material of 10,000 to 200,000, more preferably 30,000 to 150,000.

Examples of the crosslinking agent used in the condensation polymerization type silicone rubber layer include acetoxysilanes, alkoxysilanes, ketoximinesilanes, and allyloxysilanes represented by the following general formula (I). Can be.

(R ¹ ) _4-n SiX _n (I) wherein n is an integer of 2 to 4, and R ¹ is a substituted or unsubstituted alkyl group, alkenyl group or aryl group having 1 or more carbon atoms. Or a combination thereof.
Represents a functional group selected from a halogen atom, an alkoxy group, an acyloxy group, a ketoximine group, an aminooxy group, an amide group, and an alkenyloxy group. ) In the above formula,
The number n of the hydrolyzable groups is preferably 3 or 4.

Specific preferred compounds include methyltriacetoxysilane, ethyltriacetoxysilane,
Examples include, but are not limited to, vinyl triacetoxy silane, vinyl tri (methyl ethyl ketoximine) silane, tetra (methyl ethyl ketoximine) silane, and the like.

The amount of the crosslinking agent represented by the general formula (I) is preferably from 1.5 to 20% by weight, more preferably from 3 to 10% by weight, based on the total composition of the silicone rubber layer. Speaking of the quantitative ratio with polydimethylsiloxane, the molar ratio of functional group X / hydroxyl group of polydimethylsiloxane is preferably 1.5 to 10.0. When the molar ratio is 1.5 or more, there is no risk of gelation of the silicone rubber layer solution, and when the molar ratio is 10.0 or less, the physical properties of the rubber become brittle and the printing plate has scratch resistance. There is no adverse effect.

Examples of the curing catalyst include acids, alkalis, amines, metal alkoxides, metal diketenates, metal salts of organic acids, and the like. Among them, it is preferable to add an organic acid salt of a metal, particularly preferably an organic acid salt of a metal selected from tin, lead, zinc, iron, cobalt, calcium, and manganese. Specific examples of such compounds include dibutyltin diacetate, dibutyltin dioctate, and dibutyltin dilaurate. The amount of such a curing catalyst is from 0.01 to 0.01 as a solid content in the silicone rubber layer.
It is preferably 20% by weight, preferably 0.1 to 10% by weight. When the amount of the catalyst to be added is 0.01% by weight or more, the curing of the silicone rubber layer does not become insufficient, and there is no problem in the adhesiveness to the heat-sensitive layer. On the other hand, if the content is 20% by weight or less, there is no adverse effect on the pot life of the silicone rubber layer solution.

The thickness of these silicone rubber layers is 0.5 to
Preferably 20 g / m ^2, more preferably 1 to 4 g / m ^2. When the film thickness is 0.5 g / m ² or more, the ink repellency, scratch resistance, and printing durability of the printing plate can be stably exhibited, and when the film thickness is 20 g / m ² or less, the developing property,
Good ink mileage can be maintained.

Next, the heat-sensitive layer of the direct-drawing lithographic printing plate precursor that can be preferably used in the present invention is composed of a compound that absorbs laser light and generates heat, and a compound that reacts with heat to improve solubility or swelling ratio. And a group of compounds.

Compounds that generate heat by absorbing laser light include black pigments such as carbon black, titanium black, aniline black, and cyanine black, phthalocyanine, naphthalocyanine-based green pigments, carbon graphite, diamine-based metal complexes, and dithiol. Metal complex, phenol thiol metal complex, mercaptophenol metal complex, water-containing inorganic compound, copper sulfate, chromium sulfide, silicate compound, titanium oxide, vanadium oxide, manganese oxide, iron oxide, cobalt oxide, tungsten oxide And hydroxides and sulfates of these metals.

In addition, dyes that absorb infrared or near infrared rays, particularly dyes, are preferably used. Particularly preferred dyes include cyanine-based, phthalocyanine-based, naphthalocyanine-based, dithiol metal complex-based, piazurenium-based,
Squarylium-based, croconium-based, azo-based disperse dyes,
Bisazo type, bisazostilbene type, naphthoquinone type,
Anthraquinone, perylene, polymethine, indoaniline metal complex dyes, intermolecular CT, benzothiopyran, spiropyran, nigrosine, thioindigo, nitroso, quinoline, fulgide dyes, especially dyes, etc. .

Of these, cyanine dyes, polymethine dyes, and naphthalocyanine dyes are particularly preferred from the viewpoint of the absorptance of laser light.

The content of these compounds is preferably from 1 to 40% by weight, more preferably from 5 to 25% by weight, based on the total heat-sensitive layer composition. When the content is 1% by weight or more, the laser light can be efficiently absorbed. When the content is 40% by weight or less, the physical properties of the heat-sensitive layer are not adversely affected.

Reacts with the heat generated by the laser beam irradiation,
Compounds or compounds that improve solubility or swelling ratio include phenols such as phenol, cresol, and xylenol, and novolak resins and resole resins obtained by a condensation reaction of formaldehyde, and phenol.
Furfural resin, furan resin, etc., polyfunctional blocked isocyanate, polyfunctional epoxy compound, polyfunctional acrylate compound, metal chelate compound, polyfunctional aldehyde, polyfunctional mercapto compound, polyfunctional alkoxysilyl compound, polyfunctional amine compound, polyfunctional Carboxylic acid, a polyfunctional vinyl compound, a polyfunctional diazonium salt, a polyfunctional azide compound, a combination of hydrazine and the like,
A combination of a phenolic resin and a metal chelate compound is particularly preferred.

The ratio of such a compound or a group of compounds in the thermosensitive layer is preferably 20 to 20% of the total solid content of the thermosensitive layer.
It is preferably 95% by weight, more preferably 30 to 70% by weight. When the content is 20% by weight or more, the solubility or the swelling rate change due to the change in the surface layer of the heat-sensitive layer can be maintained. On the other hand, when the content is 95% by weight or less, laser light is relatively absorbed to generate heat. By maintaining the amount of the compound, the heat generation by laser irradiation does not cause a problem.

In addition, the heat-sensitive layer may contain a binder polymer, a surfactant and various additives. The content of these binders is 5 to 7 with respect to the total thermosensitive layer composition.
0% by weight is preferable, and 10 to 50% by weight is more preferable. When the content is 5% by weight or more, there is no problem in printing durability and coating properties of the coating solution, and when the content is 70% by weight or less, there is no adverse effect on image reproducibility.

The thickness of the heat-sensitive layer is 0.1 to 1 in terms of the coating layer.
0 g / m ² is preferable in terms of printing durability of the printing plate and excellent productivity because the diluting solvent is easily evaporated, and 1 to 5 g / m ^2.
Is more preferred.

A method for producing a direct-drawing waterless planographic printing plate precursor according to the present invention will be described.

Metal substrates such as aluminum and aluminum alloys,
Alternatively, use a normal coater such as a reverse roll coater, air knife coater, gravure coater, die coater, or mayer bar coater, or a spin coater such as a whey coater on a substrate such as a plastic film such as polyethylene terephthalate, and primer if necessary. After the layer composition is applied and cured by heating at 100 to 300 ° C. for several minutes or by irradiation with actinic rays, the thermosensitive layer composition is applied and dried by heating at 50 to 180 ° C. for several tens seconds to several minutes.

Thereafter, the silicone rubber composition was applied and
Heat treatment at a temperature of 0 to 200 ° C. for several minutes to obtain a silicone rubber layer.

Next, a method of making a direct-drawing waterless planographic printing plate will be described in detail.

The direct-drawing waterless planographic printing plate precursor of the present invention comprises:
After laser irradiation, development is performed using only a liquid containing water as a main component without performing any treatment using an organic solvent.

As a light source used for laser irradiation,
A laser having an emission wavelength region in the range of 300 nm to 1500 nm is used, and a semiconductor laser or a YAG laser having an emission wavelength region near the near infrared region is preferably used from the viewpoint of handleability of the plate material in a bright room. Can be Specifically, laser light having a wavelength of 830 nm or 1064 nm is preferably used for plate making. The preferred energy of laser irradiation is 50 to 500 mJ / cm ² , more preferably 250 to 400 mJ / cm ² .

Examples of the liquid containing water as a main component include water and water containing a surfactant, and water is preferable. Those containing acids, alkalis, volatile organic solvents and the like are not included in the present invention.

The printing plate after laser irradiation is developed by physically rubbing it with a brush, pad, or the like in the presence of a liquid containing water as a main component.

The development may be carried out by hand. For example, “TWL-1160” or “TWL-650” manufactured by Toray Industries, Inc.
It is preferable to use a waterless planographic automatic developing machine such as "TWL-860" or a waterless planographic washing machine such as "TWU-1160" or "TWU-860".

As a brush, a brush material having a diameter of 20 to 500 μm, which is implanted in a groove or block type metal or plastic in a row, is generally attached to a core. Alternatively, the brush material may be radially implanted in a core, or a material obtained by implanting the brush material in a base material such as a plastic sheet or cloth may be wound around the core.

The brush material is at least one selected from the group consisting of polyvinyl chloride, polyamide, polyethylene terephthalate, polybutylene terephthalate and polypropylene, so that the brush does not damage the ink repellent layer of the printing plate, and Insufficient removal of the ink repellent layer at the laser irradiation part due to insufficient power can be prevented.

Further, the number of rotations of the brush roller is 10 to 20.
00 rpm, preferably 200 to 1000 rpm. In addition, by rotating the brush roller and reciprocating in the axial direction, the effect of removing the silicone rubber layer at the laser irradiation portion is improved. The direction of rotation of the brush roller may be the same as or opposite to the direction of transport of the printing plate.

The direct-drawing waterless planographic printing plate thus obtained is dyed with a heat-sensitive layer of a laser irradiated portion serving as an image portion to give a contrast between the image portion and the non-image portion.
Enhancing image visibility is also preferably performed. As the dye used for dyeing, a water-soluble basic dye and an acid dye are particularly preferably used. Specific examples include, but are not limited to, ethyl violet, Victoria Pure Blue, Victoria Blue, methyl violet, Brilliant Basic Cyanine 6GH, and the like.

The direct-drawing waterless planographic printing plate thus dyed may be further washed with water.

[0062]

The present invention will be described in more detail with reference to the following examples.

Example 1 Production of Direct-Drawing Waterless Lithographic Printing Plate Precursor 1 A solution having the following composition was applied on a degreased aluminum plate having a thickness of 0.24 mm using a slit die coater.
After drying at 0 ° C. for 90 seconds, a heat-sensitive layer of 1.5 g / m ² was provided.

<Thermosensitive Layer 1> (a) “PROJET” 825 LDI (Avec Co., Ltd.)
ia): 11 parts by weight (b) "Nacem Titanium" (manufactured by Nippon Chemical Industry Co., Ltd., acetylacetone solution of titanium di-n-butoxide (bis-2,4-pentanedionate)): 9 parts by weight (solids concentration) (C) "Sumilite Resin" PR50622 (phenol novolak resin, manufactured by Sumitomo Durez Co., Ltd.): 60 parts by weight (d) "SAMPLEN" T1331D (polyurethane, Sanyo Chemical) Industrial Co., Ltd.): 10 parts by weight (10 as solids)
(Parts by weight) (e) m-xylylenediamine / glycidyl methacrylate / 3-glycidoxypropyltrimethoxysilane:
1/3/1 molar ratio adduct: 10 parts by weight (f) Tetrahydrofuran: 800 parts by weight (g) Dimethylformamide: 100 parts by weight

Next, a solution having the following composition was applied by a slit die coater, the drying conditions were 130 ° C. for 2 minutes, a 2.0 μm dry silicone rubber layer was provided, and a direct drawing type waterless planographic printing plate precursor 1 was prepared. I got <Silicone rubber layer 1> (a) "DBE-224" (polyalkylene oxide-modified hydrophilic silicone oil, manufactured by Gelest Co., Ltd.):
5 parts by weight (b) α, ω-divinylpolydimethylsiloxane (molecular weight: about 60,000): 100 parts by weight (c) HMS-501 (manufactured by Chisso Corp., both terminals methyl (methyl hydrogen siloxane) (dimethyl siloxane)) Copolymer Number of SiH groups / Molecular weight = 0.69 mol /
g): 7 parts by weight (d) Vinyl tri (methyl ethyl ketoxime) silane: 3 parts by weight (e) "SRX-212" (Toray Dow Corning Silicone Co., Ltd., platinum catalyst): 5 parts by weight (f) "Isopar" E (manufactured by Esso Chemical Co., Ltd.): 90
0 parts by weight (g) Tetrahydrofuran: 100 parts by weight

Development of Direct Drawing Type Waterless Lithographic Printing Plate The direct drawing type waterless planographic printing plate precursor 1 obtained as described above was mounted on a “GX-3600” (plate making machine, Toray Industries, Inc.). Laser irradiation was performed using a semiconductor laser (wavelength 830 nm) (irradiation energy 250 mJ / c).
m ^2, 2400dpi, 175lpi).

Thereafter, using a water washing machine “TWU-1160” (manufactured by Toray Industries, Inc.) for an automatic developing machine for lithographic printing plates without water, development was carried out using only water.

As a result, a direct-drawing waterless lithographic printing plate was obtained in which the portion of the silicone rubber layer irradiated with the laser beam was removed.

Evaluation of Image Reproducibility The obtained printing plate was attached to a sheet-fed offset printing machine “Sprint 25” (manufactured by Komori Corporation), and a waterless lithographic ink “Dryocolor NS” was used.
I ", indigo (manufactured by Dainippon Ink and Chemicals, Inc.) was used to print on high-quality paper (62.5 kg / chrysanthemum), and the image reproducibility of the printed matter was evaluated. there were.

Measurement of Contact Angle The obtained printing plate was subjected to “FACE contact angle meter CA-D type”.
The contact angle with water was measured using (Kyowa Interface Science Co., Ltd.). Drops of purified water having a diameter of about 1.5 mm were dropped on the silicone rubber layer in an atmosphere at room temperature of 20 ° C., and the contact angle measured 30 seconds later was 102 °.

[Comparative Example 1] A direct-drawing waterless planographic printing plate precursor 2 was prepared in exactly the same manner as in Example 1 except that the component (a) of the silicone rubber layer was omitted. Image reproducibility was 5-96%. The contact angle was 114 °.

Example 2 Preparation of Direct Drawing Type Waterless Lithographic Printing Plate Precursor 3 A solution having the following composition was applied on a degreased aluminum plate having a thickness of 0.24 mm, and dried at 200 ° C. for 2 minutes. 3g /
It provided a primer layer of m ^2. <Primer layer 1> (a) Epoxy / phenol resin "Cancoat" 90T
-25-3094 (manufactured by Kansai Paint Co., Ltd.): 15 parts by weight (b) Dimethylformamide: 85 parts by weight

A solution having the following composition was applied on this primer layer by a slit die coater,
× dried for 90 seconds, providing the heat-sensitive layer of 1.0 g / m ^2. <Thermal Sensitive Layer 2> (a) “PROJET” 825 LDI (Avec Co., Ltd.)
ia): 11 parts by weight (b) "Nacem Titanium" (manufactured by Nippon Chemical Industry Co., Ltd., acetylacetone solution of titanium di-n-butoxide (bis-2,4-pentanedionate)): 9 parts by weight (solids concentration) (C) "Sumilite Resin" PR50622 (phenol novolak resin, manufactured by Sumitomo Durez Co., Ltd.): 60 parts by weight (d) "SAMPLEN" T1331D (polyurethane, Sanyo Chemical) Industrial Co., Ltd.): 10 parts by weight (10 as solids)
(Parts by weight) (e) m-xylylenediamine / glycidyl methacrylate / 3-glycidoxypropyltrimethoxysilane:
1/3/1 molar ratio adduct: 10 parts by weight (f) Tetrahydrofuran: 800 parts by weight (g) Dimethylformamide: 100 parts by weight

Next, a solution having the following composition was applied by a slit die coater, the drying conditions were set at 130 ° C. for 2 minutes, a silicone rubber layer having a dry film thickness of 2.0 μm was provided, and “Lumirror” (Toray Industries, Inc.) And a polyethylene terephthalate film) were laminated to obtain a direct-drawing waterless planographic printing plate precursor 3. <Silicone rubber layer 3> (a) "Light acrylate" 1,9ND-A (manufactured by Kyoeisha Chemical Co., Ltd.): 5 parts by weight (b) polydimethylsiloxane (molecular weight of about 50,000
0, both terminal hydroxyl groups): 100 parts by weight (c) Vinyl tris (methylethyl ketoxime) silane (crosslinking agent): 4 parts by weight (d) Dibutyltin diacetate (tin catalyst, curing catalyst):
0.01 parts by weight (e) "Isopar" E (manufactured by Esso Chemical Co., Ltd.): 95
0 parts by weight (f) Tetrahydrofuran: 50 parts by weight

When evaluated exactly in the same manner as in Example 1, the image reproducibility was 2-98%. The contact angle is 102
°.

Comparative Example 2 A direct-drawing waterless planographic printing plate precursor 4 was prepared in exactly the same manner as in Example 2 except that the component (a) of the silicone rubber layer was removed and the film was not laminated. When evaluated similarly, the image reproducibility was 5 to 96%. The contact angle was 112 °.

Example 3 Preparation of Direct Drawing Type Waterless Lithographic Printing Plate Precursor 5 A solution having the following composition was applied on a degreased aluminum plate having a thickness of 0.24 mm by a slit die coater.
After drying at 0 ° C. for 90 seconds, a heat-sensitive layer of 1.5 g / m ² was provided. <Thermal Sensitive Layer 1> (a) "KAYASORB" PS101 (manufactured by Nippon Kayaku Co., Ltd.): 11 parts by weight (b) "Nasem Titanium" (manufactured by Nippon Chemical Industry Co., Ltd., titanium di-n-butoxide (bis-2, Acetone acetone solution of 4-pentanedionate): 9 parts by weight (calculated as a solid content concentration of 40% by weight; solids content of 9 parts by weight) (D) "SAMPLEN" T1331D (polyurethane, manufactured by Sanyo Chemical Industries, Ltd.): 30 parts by weight (solid content: 30)
(Parts by weight) (e) m-xylylenediamine / glycidyl methacrylate / 3-glycidoxypropyltrimethoxysilane:
1/3/1 molar ratio adduct: 10 parts by weight (f) "Light acrylate" 1,9ND-A (manufactured by Kyoeisha Chemical Co., Ltd.): 5 parts by weight (g) Tetrahydrofuran: 800 parts by weight (h) dimethylformamide : 100 parts by weight

Next, a solution having the following composition was applied by a slit die coater, a drying condition was set at 130 ° C. × 2 minutes, a silicone rubber layer having a dry film thickness of 2.0 μm was provided, and a “Lumirror” (Toray Industries, Inc.) And a polyethylene terephthalate film) were laminated to obtain a direct-drawing waterless planographic printing plate precursor 5. <Silicone Rubber Layer 5> (a) Polydimethylsiloxane (molecular weight of about 50,000
0, both terminal hydroxyl groups): 100 parts by weight (b) Ethyltris (acetoxy) silane (crosslinking agent):
14 parts by weight (c) dibutyltin diacetate (tin catalyst, curing catalyst):
0.01 parts by weight (d) "Isopar" E (manufactured by Esso Chemical Co., Ltd.): 95
0 parts by weight (e) Tetrahydrofuran: 50 parts by weight

When evaluated exactly in the same manner as in Example 1, the image reproducibility was 2-98%. The contact angle is 100
°.

[0080]

According to the present invention, a direct drawing type waterless planographic printing plate precursor which can be developed with water only without using any organic solvent is obtained.

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Claims (1)

[Claims] 1. A direct-drawing waterless planographic printing plate precursor having at least a heat-sensitive layer and a silicone rubber layer in this order on a substrate, wherein the contact angle of water with respect to the silicone rubber layer is 1
A direct-drawing waterless lithographic printing plate precursor characterized by being 10 ° or less.