JPH09244228A - Planographic original plate requiring no dampening water - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a waterless original plate having high sensitivity and capable of laser beam recording by successively laminating a primer layer contg. fine hollow polymer particles, an adhesiveness reducing layer and a silicone rubber layer on a substrate. SOLUTION: A primer layer contg. fine hollow polymer particles, an adhesiveness reducing layer and a silicone rubber layer are successively laminated on a substrate. The adhesiveness reducing layer is a photothermic conversion layer and converts laser light into heat and reduces the adhesiveness of the silicone rubber layer to the primer layer by the heat at the irradiated part. Since the fine hollow polymer particles are used in the primer layer, laser light reflectance is increased, laser light is effectively used and energy loss due to the diffusion of heat generated in the photothermic conversion layer by exposure to laser light into the substrate is reduced. The fine hollow polymer particles are fine particles having internal voids and are liable to reflect light at the interface between the polymer and air by the difference in refractive index between them.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a highly sensitive fountain solution-free lithographic printing plate precursor (hereinafter referred to as a waterless lithographic printing plate precursor) capable of printing without dampening water by heat mode recording using a laser beam.

[0002]

2. Description of the Related Art Conventional printing methods that require dampening water make it difficult to control the delicate balance between dampening water and ink.
There have been major problems such as emulsification of the ink and mixing of the ink with the fountain solution, resulting in defective ink density and scumming, which causes wasted paper. In contrast, waterless lithographic printing plates have many advantages because they do not require fountain solution.

On the other hand, in recent years, due to rapid progress in output systems such as prepress systems, imagesetters and laser printers, printed images are converted into digital data,
New plate making methods such as computer tow plate, computer tow cylinder, etc. have come to be proposed for obtaining printing plates, and new types of printing materials for these printing systems are desired and are being developed. ing. Examples of a waterless planographic printing plate that can be formed by laser writing include JP-B-42-21879.
JP-A-50-158405, JP-A-5-9400
No. 8, JP-A-6-55723, JP-A-6-6-1.
86750, JP-A-7-314934, U
S5,353,705 and WO-940128.
0 publications and the like. These include a layer containing a laser light absorber such as carbon black and a self-oxidizing binder such as nitrocellulose that converts light into heat (hereinafter referred to as a photothermal conversion layer) or an ink repellent property on a metal thin film layer. It is described that a silicone rubber layer is provided, and a part of the silicone rubber layer is removed by laser irradiation to make the ink adherent, and printing is performed without water. However, these plate materials have low sensitivity and a large amount of light energy is required to remove the silicone rubber layer. Therefore, in order to write an image by high-speed scanning, a large-power laser light source is required, which has a drawback that the image recording apparatus becomes large and expensive, and its improvement is strongly desired. .

[0004]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a highly sensitive waterless planographic original plate capable of laser recording.

[0005]

Means for Solving the Problems As a result of diligent studies on a method for producing a highly sensitive waterless planographic original plate capable of being laser-written, the present inventors have found that a primer layer containing hollow polymer fine particles on a support and a laser beam were used. A dampening characterized in that a layer (photothermal conversion layer) that converts into heat and reduces the adhesiveness at any part of the primer layer and the silicone rubber layer due to the heat and a silicone rubber layer are laminated in this order. The object of the present invention has been achieved by a waterless planographic original plate. The present invention, by using hollow fine particles in the primer layer, enhances the reflectance of laser light and effectively uses laser light, and the heat generated in the photothermal conversion layer by laser light exposure diffuses to the support to reduce energy loss. I think that it was achieved by suppressing the occurrence.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. "Support" The support of the waterless planographic original plate of the present invention must have flexibility so that it can be set in an ordinary printing machine and at the same time withstand a load applied during printing. Therefore, as a typical substrate, a metal plate such as aluminum, an aluminum-containing alloy (for example, an alloy of aluminum with a metal such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, or nickel), Plastic film such as polyethylene terephthalate, polyethylene naphthalate, paper or polyethylene,
Examples thereof include a composite sheet laminated with a plastic film such as polypropylene. The thickness of the support is appropriately 25 μm to 3 mm, preferably 75 μm to 500 μm, but the optimum thickness varies depending on the type of support used and printing conditions. Generally 100 μm
To 300 μm is most preferable.

"Primer layer" The hollow polymer fine particles used in the present invention are resin particles having voids inside, and due to the difference in the refractive index between air and the resin polymer, light is easily reflected at the interface between them, and the particles become white. It is visible and is generally used as a hiding agent for paints or a white pigment with a high hiding power.
These are used to form seed particles by copolymerizing unsaturated carboxylic acid by emulsion polymerization and then forming a particle surface layer.
Cover polymerization using an ethylenically unsaturated monomer, after the completion of the polymerization, a method of swelling the particles by neutralizing the unsaturated carboxylic acid copolymerized with a volatile base such as ammonia or unsaturated carboxylic acid It is prepared by neutralizing the carboxyl group of the contained copolymer latex with a base and then adding an acid. Specifically, for example, those sold under the trade names of "ROPAK" (manufactured by Rohm and Haas Co.), "Grandall" (manufactured by Dainippon Ink and Chemicals Co., Ltd.), and JP-A-56-32513. Hollow polymer particles described in JP-A No. 60-223873, JP-A No. 64-1704, and JP-A No. 7-102424 can be used. The particle size is preferably 0.05 μm to 3 μm, more preferably 0.05 μm to 1 μm. These hollow polymer particles are coated on a support in a state of being mixed with a water-soluble polymer or dispersed in an oil-soluble polymer.

The binder used in the primer layer of the present invention is, for example, one obtained by exposing and curing various photosensitive polymers as disclosed in JP-A-60-22903, and JP-A-62-162. The epoxy resin disclosed in Japanese Patent No. 50760 is heat-cured, the gelatin disclosed in Japanese Patent Application Laid-Open No. 63-133151 is hardened, and further disclosed in Japanese Patent Application Laid-Open No. 3-200965. Examples thereof include those using a urethane resin and a silane coupling agent, and those using the urethane resin disclosed in JP-A-3-273248. In addition, those obtained by hardening gelatin or casein are also effective. Furthermore, in the primer layer, polyvinyl alcohol, modified polyvinyl alcohol, polyvinylpyrrolidone, polyurethane, polyamide, styrene / butadiene rubber, carboxy modified styrene / butadiene rubber, acrylonitrile / butadiene rubber, carboxy modified acrylonitrile / butadiene rubber, polyisoprene, Polymers such as acrylate rubber, polyethylene, chlorinated polyethylene, chlorinated polypropylene, vinyl chloride / vinyl acetate copolymer, nitrocellulose, halogenated polyhydroxystyrene, and chlorinated rubber may be added. Further, these primer layers may contain additives such as an adhesion aid (for example, a polymerizable monomer, a diazo resin, a silane coupling agent, a titanate coupling agent or an aluminum coupling agent) and a dye.
After the application, it can be cured by exposure.
The proportion of the hollow polymer fine particles in the primer layer is 5% by weight to 65% by weight of the total solids of the primer layer, preferably 10% by weight to 55% by weight, more preferably 20% by weight.
% To 50% by weight. The primer layer is also useful as an ink receiving layer for the silicone layer-removed portion, and is particularly useful when the support is a non-ink receiving material such as a metal support. Further, the primer layer also has a role as a cushion layer for relieving pressure on the silicone layer during printing. Generally, the coating amount of the primer layer is appropriately in the range of 0.1 to 10 g / m ² as dry weight, preferably 0.2 to 8 g / m ² , and more preferably 0.5 to 5 g.
g / m ² .

"Light-to-heat conversion layer" The light-to-heat conversion layer used in the present invention converts the laser light used for writing into heat, and the heat causes adhesiveness at any part of the primer layer and the silicone rubber layer. It is a layer having a function of decreasing, and a known photothermal conversion layer having these functions can be used. In the photothermal conversion layer of the present invention, the laser light energy used for recording is absorbed and converted into heat energy, which results in combustion, melting, decomposition, vaporization,
As a result of reaction such as explosion and physical change, the adhesion is lowered at any part between the primer layer and the silicone rubber layer. As a photothermal conversion material,
When the laser light source is an infrared laser, various organic and inorganic materials that absorb light of the wavelength used for writing lasers, such as infrared absorbing dyes, infrared absorbing pigments, infrared absorbing metals, and infrared absorbing metal oxides can be used. Known to be. These materials are in the form of a single film,
Alternatively, it is used in the form of a mixed film with other components such as a binder and an additive. In the case of a single film, aluminum,
Titanium, tellurium, chromium, tin, indium, bismuth,
Metals and alloys such as zinc and lead, metal oxides, metal carbides, metal nitrides, metal borides, metal fluorides and organic dyes can be formed on the support by vapor deposition, sputtering or the like. In the case of a mixed film, the light-to-heat conversion material can be formed by dissolving or dispersing the light-to-heat conversion material together with other components by a coating method.

(Photothermal conversion agent) As the photothermal conversion agent, various carbon blacks such as acidic carbon black, basic carbon black and neutral carbon black as organic pigments, and surface modification or surface coating for improving dispersibility, etc. "Infrared sensitizing dyes" for various carbon blacks, nigrosine, and organic dyes (Plenum Press, New by Matsuoka)
York, NY (1990)), US-4833124, EP-32.
1923, US-4772585, US-494214
1, US-4948776, US-4948777, U
S-4948778, US-495039, US-4
912083, US-4955252, US-5023
Examples of various compounds and metals or metal oxides described in the specification of No. 229 are aluminum, indium tin oxide, tungsten oxide, manganese oxide, titanium oxide, and the like.
In addition, conductive polymers such as polypyrrole and polyaniline can also be used.

(Binder) As the binder used when the photothermal conversion layer is formed as a mixed film, known binders that dissolve or disperse the photothermal conversion material are used. Examples of these include nitrocellulose, cellulose such as ethyl cellulose, cellulose derivatives, polymethyl methacrylate, acrylic acid esters such as polybutyl methacrylate, homopolymers and copolymers of methacrylic acid esters, polystyrene, α-methyl styrene and the like. Homopolymer or copolymer of styrene monomer. Various synthetic rubbers such as isoprene and styrene-butadiene, homopolymers of vinyl esters such as polyvinyl acetate and copolymers such as vinyl acetate-vinyl chloride, various condensation polymers such as polyurea, polyurethane, polyester and polycarbonate, and , "J. Ima
ging Sci., P59-64, 30 (2), (1986) (Frechet et al.) "and" Polymers in Electronics (Symposium Series, P11,
242, T. Davidson, Ed., ACS Washington, DC (1984) (Ito,
Willson) "," Microelectronic Engineering, P3-10,1
3 (1991) (E. Reichmanis, LFThompson) and the like, and the binders used in so-called “chemical amplification systems” can be used.

(Additive) When the photothermal conversion layer is formed as a mixed film, an additive can be used in addition to the photothermal conversion agent and the binder. These additives improve the mechanical strength of the photothermal conversion layer, improve the laser recording sensitivity, improve the dispersibility of the dispersion in the photothermal conversion layer, and adjoin the support and the primer layer. It is added according to various purposes such as improving the adhesion to the layer.
For example, a means for crosslinking the photothermal conversion layer can be considered in order to improve the mechanical strength of the photothermal conversion layer, and in this case, various crosslinking agents are added. In order to improve the laser recording sensitivity, it is conceivable to add a known compound that decomposes by heating to generate a gas. In this case, the laser recording sensitivity can be improved by the rapid volume expansion of the photothermal conversion layer.
(Examples of these additives include dinitropentamethylenetetramine, N, N′-dimethyl-N, N′-dinitrosoterephthalamide, p-toluenesulfonylhydrazide, 4,4-oxybis (benzenesulfonylhydrazide), It is possible to use diamidobenzene etc.) In addition, a known compound that decomposes by heating to form an acidic compound can be used as an additive. By using these in combination with a chemical amplification type binder, it is possible to greatly reduce the decomposition temperature of the constituents of the photothermal conversion layer and consequently improve the laser recording sensitivity. (Examples of these additives include various iodonium salts, sulfonium salts, phosphonium tosylate, oxime sulfonates, dicarbodiimide sulfonates, triazines, etc.) Carbon as a photothermal conversion agent When a pigment such as black is used, the degree of dispersion of the pigment may affect the laser recording sensitivity, and various pigment dispersants are used as additives. A known adhesion improver (for example, a silane coupling agent, a titanate coupling agent, etc.) may be added to improve the adhesiveness. In addition, various additives such as a surfactant for improving coating properties are used as needed.

(Film Thickness) With respect to the film thickness of the light-heat conversion layer, a thin film can be formed by a vapor deposition method, a sputtering method or the like when it is a single film. In this case, the film thickness is 50 ° to 1000 °, preferably 100 ° to 800 °. The mixed film is formed by coating. In this case, the film thickness is 0.05 μm to 10
μm, preferably 0.1 μm to 5 μm. If the photothermal conversion layer is too thick, unfavorable results such as a decrease in laser recording sensitivity are given.

"Silicone Layer" The crosslinked silicone rubber layer used in the present invention is a film formed by curing the following composition A or B. Composition A (a) 100 parts by weight of diorganopolysiloxane (b) 3 to 70 parts by weight of condensation type crosslinking agent (c) 0.01 to 40 parts by weight The diorganopolysiloxane of the component (a) has the following general formula: In the polymer having a repeating unit represented by the formula, R ¹ and R ² are an alkyl group having 1 to 10 carbon atoms, a vinyl group, an aryl group, and may have other appropriate substituents. Generally 60% of R ¹ and R ²
The above are preferably a methyl group, a vinyl halide group, a halogenated phenyl group, or the like.

[0015]

Embedded image

It is preferable to use a diorganopolysiloxane having hydroxyl groups at both ends. The component (a) has a number average molecular weight of 3,000 to 1
0,000, more preferably 5,000 to 7
It is 0000. Component (b) may be of any type as long as it is a condensation type, but is preferably one represented by the following general formula. R ¹ _m · Si · X _n (m + n = 4, n is 2 or more) Here, R ¹ has the same meaning as R ¹ described above, and X is a substituent as shown below. Cl, Br, halogen H or OH, such as ^{I, -OCOR 3, -OR 3,} -O-N
^{= C (R 4) (R} 5), - N (R 4) (R 5) organic substituent such as. Here, R ³ represents an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 20 carbon atoms, and R ⁴ and R ⁵ represent an alkyl group having 1 to 10 carbon atoms. Component (c) includes metal carboxylates such as tin, zinc, lead, calcium and manganese, for example, dibutyl laurate, lead octylate, lead naphthenate, etc., or known catalysts such as chloroplatinic acid, etc. .

Composition B (d) 100 parts by weight of diorganopolysiloxane having an addition-reactive functional group (e) 0.1 to 25 parts by weight of organohydrogenpolysiloxane (f) 0.00001 to 1 part by weight of addition catalyst The diorganopolysiloxane having an addition-reactive functional group of the component (d) is an organopolysiloxane having at least two alkenyl groups (more preferably vinyl groups) directly bonded to a silicon atom in one molecule. The group may be at the terminal or in the middle of the molecular weight, and the organic group other than the alkenyl group is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or an aryl group. Component (d) may optionally have a trace amount of hydroxyl groups. The component (d) has a number average molecular weight of 3,000 to 100,00.
0, more preferably 5,000 to 70,000
It is. As the component (e), polydimethylsiloxane having both terminal hydrogen groups, α, ω-dimethylpolysiloxane, (methylsiloxane) (dimethylsiloxane) copolymer having both terminal methyl groups, cyclic polymethylsiloxane, both terminal trimethylsilyl groups And poly (methyl siloxane) (methyl siloxane) copolymers having trimethylsilyl groups at both ends are exemplified. The component (f) is arbitrarily selected from known compounds, and is particularly preferably a platinum compound, such as platinum alone, platinum chloride, chloroplatinic acid, and olefin-coordinated platinum. For the purpose of controlling the curing rate of these compositions, vinyl group-containing organopolysiloxane such as tetracyclo (methylvinyl) siloxane, carbon-carbon triple bond-containing alcohol,
Acetone, methyl ethyl ketone, methanol, ethanol
It is also possible to add a crosslinking inhibitor such as propylene glycol or propylene glycol monomethyl ether. The silicone rubber layer may contain silica, calcium carbonate, and
Fine powders of inorganic materials such as titanium oxide, silane coupling agents, adhesion aids such as titanate coupling agents and aluminum coupling agents may be added. The silicone rubber layer in the present invention has a problem that the ink repelling property is reduced when the thickness is small and scratches are likely to occur, and the image reproducibility is deteriorated when the thickness is large, the thickness is preferably 0.5 to 5 g / m ^2, more preferably 1 to 3 g / m ^2.

In the present invention, laser light is used to expose a waterless lithographic original plate. The laser used is not particularly limited as long as it gives an exposure amount necessary for the adhesive force to be sufficiently removed so that the silicone rubber layer is peeled and removed, and a gas laser such as an Ar laser or a carbon dioxide gas laser is used. , Solid-state lasers such as YAG lasers, and semiconductor lasers can be used. A laser with a normal output of 50 mW or higher is required. Semiconductor lasers and semiconductor-excited solid-state lasers (such as YAG lasers) are preferably used in terms of practicality such as maintainability and price. The recording wavelength of these lasers is in the infrared wavelength region, and an oscillation wavelength of 800 nm to 1100 nm is often used. In addition, JP-A-6-186
It is also possible to perform exposure using the imaging apparatus described in Japanese Patent Publication No. 750. The film for protecting the surface of the silicone rubber layer may be used as it is at the time of laser exposure, or may be exposed after being peeled off.

As the developing solution used in the present invention, a known developing solution for a waterless planographic original plate can be used, but from the viewpoint of safety, water or an aqueous solution of a water-soluble organic solvent containing water as a main component is preferable. . In consideration of safety and flammability, the concentration of the water-soluble solvent is preferably less than 40% by weight. Known compounds include, for example, aliphatic hydrocarbons (hexane, heptane, "Isopar E, H, G" (manufactured by Esso Chemical Co., Ltd.) or gasoline, kerosene, etc.), aromatic hydrocarbons (toluene, xylene, etc.). ) Or a halogenated hydrocarbon (trichlene, etc.) to which the following polar solvent is added, or the polar solvent itself: alcohols (methanol, ethanol, propanol, isopropanol, benzyl alcohol, ethylene glycol monomethyl ether, 2-ethoxyethanol, Diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, polyethylene glycol monomethyl ether -Ketones (acetone, methyl ethyl ketone, etc.)-Esters (ethyl acetate, methyl lactate, butyl lactate, etc.)
Propylene glycol monomethyl ether acetate,
Diethylene glycol acetate, diethyl phthalate, etc.) Others (triethyl phosphate, tricresyl phosphate, etc.) Also, water can be added to the organic solvent-based developer or the organic solvent can be added to water by using a surfactant or the like. Solubilized or even alkaline agent (for example,
Examples thereof include those to which sodium carbonate, diethanolamine, sodium hydroxide, etc.) have been added, or simply water (tap water, pure water, distilled water, etc.) and the like.

The development can be carried out by a known method such as rubbing the plate surface with a developing pad containing the above-mentioned developing solution, or pouring the developing solution onto the plate surface and then rubbing it with a developing brush in water. . The developer can be developed at any temperature, but is preferably from 10C to 50C. As a result, the silicone rubber layer in the image area is removed, and that area becomes the ink receiving area. The above-described development processing, or subsequent washing with water and drying processing can be performed by an automatic processor. A preferable automatic processor is disclosed in JP-A-2-220.
No. 061 publication. Further, the waterless planographic original plate of the present invention can be developed by adhering the adhesive layer to the surface of the silicone rubber layer and then peeling off the adhesive layer. As the adhesive layer, any known adhesive layer that can adhere to the surface of the silicone rubber layer can be used. A flexible support provided with these adhesive layers is commercially available. For example, Sumitomo 3M's "Scotch tape # 851A"
It is commercially available under the trade name. When the plates thus processed are stacked and stored, it is preferable to insert and insert a slip sheet to protect the plates.

[0021]

EXAMPLES The present invention will be described in more detail by way of examples. However, the present invention is not limited to the following examples. Example 1 and Comparative Example 1 (Preparation of primer layer) A polyethylene terephthalate film having a thickness of 180 μm was coated with a primer layer coating solution having the following composition so as to have a dry film thickness of 2 μm.
The primer layer of was formed. -Lactate casein (manufactured by New Zealand Murray Coulburn Cooperative Co. Ltd.) 50 g-Anhydrous sodium carbonate 2.6 g-Grandall PP-1000 (manufactured by Dainippon Ink and Chemicals, Inc., hollow polymer particles, solid content concentration 45%) 100 g・ Nikkor OTC-100S (manufactured by Nikko Chemicals, anionic surfactant) 1.2 g ・ γ-glycidoxypropyltrimethoxysilane 3.0 g ・ CH ₂ = CHSO ₂ CH ₂ CH (OH) CH ₂ SO ₂ CH = CH ₂ 3.0 g-Pure water 500 g The primer layer of Comparative Example 1 was prepared in the same manner as in Example 1 except that the hollow polymer particles were removed from the primer layer coating solution.

(Preparation of Carbon Black Dispersion) After dispersing the following mixture for 30 minutes with a paint shaker,
The glass beads were filtered off to prepare a carbon black dispersion liquid.・ Carbon black (# 40 manufactured by Mitsubishi Carbon Co., Ltd.) 5.0 g ・ Crisbon 3006LV (Polyurethane manufactured by Dainippon Ink and Chemicals, Inc.) 4.0 g ・ Nitrocellulose (containing 30% of n-propanol) 1.3 g ・ Solspers S27000 (manufactured by ICI) 0.4 g-Propylene glycol monomethyl ether 45 g-Glass beads 160 g (Formation of photothermal conversion layer) On the primer layer of Example 1 and Comparative Example 1 described above, the following coating solution was dried to a film thickness of 1 μm. Was applied to form a photothermal conversion layer. -55 g of the above carbon black dispersion-Nitrocellulose (containing 30% of n-propanol) 5 g-Crisbon 3006LV (Polyurethane manufactured by Dainippon Ink and Chemicals, Inc.) 20 g-Propylene glycol monomethyl ether 200 g (Formation of silicone rubber layer) The coating liquid of (1) was applied onto the photoheat exchange layer, heated (130 ° C., 1 minute), and dried to form an addition type silicone rubber layer having a dry film thickness of 2 μm.・ Α, ω-Divinylpolydimethylsiloxane (Polymerization degree: 500) 9g ・ (CH ₃ ) ₃ SiO (SiH (CH ₃ ) O) ₈ -Si (CH ₃ ) ₃ 0.8g ・ Olefin-chloroplatinic acid 0.001g・ Control agent [HC≡CC (CH ₃ ) ₂ -O-Si (CH ₃ ) ₃ ] 0.3 g ・ Isopar G (manufactured by Esso Chemical Co., Ltd.) 120 g

6 μm polyethylene terephthalate was laminated on the surface of the silicone rubber layer obtained as described above. After peeling off the cover film of the obtained waterless planographic original plate of the invention, a semiconductor excitation Y having a wavelength of 1064 nm, a beam diameter of 40 μm (1 / e ² ) and an output of 500 mW
Continuous lines were written by changing the writing speed using an AG laser. Then, the plate surface was wiped with a developing pad containing isopropanol to remove the silicone rubber layer in the laser-irradiated portion. The plate surface energy that the silicone rubber layer in the irradiated part can remove as a continuous line is 95 mJ / cm ² in the waterless planographic original plate containing the hollow polymer particles in the primer layer of the present invention, and the hollow polymer particles in the primer layer of Comparative Example 1 are 182 mJ / cm ^{2 for} waterless planographic printing plate that does not contain
Met. From this, it is clear that the waterless planographic original plate of the present invention has high sensitivity.

Example 2 and Comparative Example 2 (Preparation of Primer Layer) A 180 μm thick corona-treated polyethylene terephthalate film was coated with a primer layer coating solution having the following composition to give a dry film thickness of 3 μm. Two primer layers were formed.・ Acid-treated gelatin 950 (manufactured by Nitta Gelatin) 50 g ・ Grandall PP-1000 (manufactured by Dainippon Ink and Chemicals, Inc., hollow polymer particles, solid content concentration 45%) 80 g ・ Nikkor OTC-100S (manufactured by Nikko Chemicals, anion) Surfactant) 1.2 g-CH ₂ = CHSO ₂ CH ₂ CH (OH) CH ₂ SO ₂ CH = CH ₂ 3.0 g-Pure water 500 g The primer layer of Comparative Example 2 was hollow polymer particles prepared from the above coating solution for the primer layer. It was prepared in the same manner as in Example 2 except that

(Formation of photothermal conversion layer) On a corona-treated polyethylene terephthalate film having a thickness of 180 μm,
Under the condition of 5 × 10 ⁻⁵ Torr, titanium was OD = 0.5 (106
4 nm) was deposited. (Formation of Silicone Rubber Layer) The following coating solution was prepared, coated on the titanium vapor deposition surface, heated (110 ° C., 1 minute) and dried to form a condensed silicone rubber layer having a dry film thickness of 2 μm. . -Dimethylpolysiloxane having hydroxyl groups at both ends (Polymerization degree 700) 9g-Methyltriacetoxysilane 0.5g-Dibutyltin dioctanate 0.2g-Isopar G (manufactured by Esso Chemical Co., Ltd.) 160g Obtained as described above 6 on the surface of the silicone rubber layer
μm polyethylene terephthalate was laminated.

After peeling off the cover film of the waterless planographic original plate of the present invention obtained, a semiconductor excited Y having a wavelength of 1064 nm, a beam diameter of 40 μm (1 / e ² ) and an output of 500 mW.
Continuous lines were written by changing the writing speed using an AG laser. After that, the plate surface was wiped with a developing pad soaked with water to remove the silicone rubber layer in the laser irradiation portion. The plate surface energy that the silicone rubber layer in the irradiated portion can remove as a continuous line is 106 mJ / cm ² for the waterless planographic original plate containing hollow polymer particles in the primer layer of the present invention, and the hollow polymer particles in the primer layer of Comparative Example 2 are The waterless planographic original plate containing no water was 198 mJ / cm ² . From this, it is clear that the waterless planographic original plate of the present invention has high sensitivity.

Example 3 (Support) An aluminum support having a thickness of 0.24 mm was coated with a coating solution having the following composition so as to have a dry film thickness of 2 μm, heated (100 ° C., 1 minute) and dried. To form a primer layer. -Samprene IB1700D (polyurethane manufactured by Sanyo Kasei Co., Ltd.) 10 g-Hexafluorophosphate 0.1 g of polycondensation polymer of p-diazodiphenylamine and paraformaldehyde-Grandol Exp PP-207S 8 g-Defencer MCF323 (Dainippon Nihon) Ink Chemical Industry Co., Ltd., surfactant) 0.03g-Propylene glycol methyl ether acetate 50g-Methyl lactate 20g-Pure water 1g After that, Neark FT261V UDNS ULTRA-PLUS FLIPTO
Exposure was performed 20 counts using a P PLATE MAKER vacuum exposure machine.

(Formation of Light-to-heat Conversion Layer) The following liquid mixture was dispersed in a paint shaker for 30 minutes, and then glass beads were filtered off to prepare a light-to-heat conversion layer coating liquid. This coating solution was applied onto the primer layer so as to have a dry film thickness of 2 μm to form a photothermal conversion layer. -Carbon black (# 40 manufactured by Mitsubishi Carbon Co., Ltd.) 5g-Nipporan 2304 (polyurethane manufactured by Nippon Polyurethane Company) 20g-Solspers S2000 (manufactured by ICI) 0.27g-Solspers S12000 (manufactured by ICI) 0.22g-Nitrocellulose (Containing 30% of n-propanol) 7.2 g-Methyl ethyl ketone 50 g-Propylene glycol monomethyl ether 50 g-Glass beads 160 g (Formation of silicone rubber layer) The following coating solution was applied on the light-heat exchange layer and heated (110 ° C, 1 minute) and dried to form an addition type silicone rubber layer having a dry film thickness of 2 μm.・ Α, ω-Divinylpolydimethylsiloxane (polymerization degree: about 700) 9.00 g ・ (CH ₃ ) ₃ -Si-O- (SiH (CH ₃ ) -O) ₈ -Si (CH ₃ ) ₃ 1.35 g ・polydimethylsiloxane (polymerization degree: about 8000) 0.30 g · olefin - chloroplatinic acid 0.001 g · inhibitor _{[HC≡CC (CH 3) 2 -O} -Si (CH 3) 3] 0.2g · Isopar G ( Esso Chemical Co., Ltd. 140 g 6 on the surface of the silicone rubber layer obtained as described above.
μm polyethylene terephthalate was laminated.

After peeling off the cover film of the obtained waterless planographic original plate, the wavelength was 1064 nm and the beam diameter was 40 μm.
Writing of continuous lines was performed using a (1 / e ² ) semiconductor-excited YAG laser. Recording energy is 300mJ /
cm ² . Then, Scotch tape # 851A (manufactured by Sumitomo 3M Limited) was attached to the surface of the silicone rubber layer and then peeled off to remove the silicone rubber layer at the laser-irradiated portion. On the other hand, the silicone layer in the unirradiated area was not removed but was retained on the surface of the waterless planographic original plate, and a silicone image having a sharp edge could be formed. In addition, the waterless planographic original plate outputs 110 mW, wavelength 825 nm, beam diameter 1
Writing was performed at a main operation speed of 5 m / sec using a semiconductor laser of 0 μm (1 / e ² ), and the same treatment was performed to remove the silicone rubber layer in the laser irradiation portion. The resolution was 7 μm and a waterless planographic printing plate with sharp edges was formed. When halftone dots of 200 lines were formed under these recording conditions, halftone dot area ratios of 2% to 98% could be formed on the plate. Further, when the obtained waterless planographic printing plate was printed using a printing machine, 100,000 good printed matters without stains were obtained.

[0030]

INDUSTRIAL APPLICABILITY The waterless planographic original plate of the present invention is capable of heat mode recording with a laser beam and has high sensitivity.

Claims (1)

[Claims] 1. A primer layer containing hollow polymer fine particles on a support, a layer which converts laser light into heat and reduces the adhesion at any part of the primer layer and the silicone rubber layer by the heat, and silicone. A lithographic original plate that does not require dampening water, characterized by laminating rubber layers in this order.