JPH0968794A - Production of planographic printing plate requiring no dampening water - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a positive type waterless planographic printing plate capable of writing with visible light laser and having high sensitivity and satisfactory tone reproducibility. SOLUTION: In this photosensitive planographic printing plate obtd. by successively laminating a primer layer, a photopolymerizable photosensitive layer and a silicone rubber layer on a substrate, the photosensitive layer contains at least one kind of compd. having >=400nm λmax as a constituent of a photopolymn. initiator system. This planographic printing plate is exposed using visible light laser as a light source.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive lithographic printing plate which does not require a fountain solution, which is obtained by laminating a primer layer, a photopolymerizable photosensitive layer and a silicone rubber layer in this order on a support, particularly an argon laser, YAG. -A method for producing a lithographic printing plate not requiring fountain solution, which comprises exposing using a visible light laser such as an SHG laser.

[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, a planographic printing plate that does not require dampening water (hereinafter referred to as "waterless planographic printing plate")
(Also referred to as) has many advantages because it does not require fountain solution. Regarding a waterless planographic printing plate for performing planographic printing without using such dampening water, for example, Japanese Patent Publication No.
4-23042, JP-B-46-16044, JP-B-54-26923, JP-B-56-14976, JP-B-56-23150, JP-B-61-54222, JP-A-58-215411, JP-A-58-215411 2-16561,
Various types have been proposed in Japanese Patent Laid-Open No. 2-236550. Among them, a plate-making method in which a primer layer, a photosensitive layer and a silicone rubber layer are applied in this order on a support and only the unexposed area of the silicone rubber layer is peeled off in the development to form an image area has an extremely excellent performance. Have

On the other hand, in recent years, due to the rapid progress of output systems such as prepress systems, imagesetters and laser printers, computer toe plates,
New plate making methods such as computer tow cylinders have been proposed, and new types of printing materials for these printing systems are desired and are being developed. However, a printing material having sufficient sensitivity to a visible light laser has not yet been found, and the waterless planographic printing plate described above has a sensitivity to visible light of 400 nm or more as compared with sensitivity to ultraviolet light of 400 nm or less. Remarkably low.

[0004]

SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a method for producing a positive type waterless lithographic printing plate which is writable by a visible light laser and has high sensitivity and good tone reproducibility.

An object of the present invention is to laminate a primer layer, a photopolymerizable photosensitive layer and a silicone rubber layer on a support in this order, and the photopolymerizable photosensitive layer is 4 layers.
A dampening-water-free lithographic printing plate, which is characterized by containing at least one compound having a λmax of 00 nm or more, and which is exposed to a visible light laser as a light source. And a method of manufacturing a printing plate.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The waterless lithographic printing 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 the load applied during printing.
Therefore, as a typical support, a coated paper, a metal plate such as aluminum, a plastic film such as polyethylene terephthalate, rubber or a composite thereof can be mentioned, and more preferably aluminum and an aluminum-containing alloy. (For example, silicon,
Alloys with metals such as copper, manganese, magnesium, chromium, zinc, lead, bismuth, and nickel with aluminum)
Alloy.

In the present invention, it is desirable to provide a primer layer between the support and the photosensitive layer. As the primer layer used in the present invention, various types can be used for improving the adhesion between the support and the photopolymerizable photosensitive layer, preventing halation, dyeing an image and improving printing characteristics.
For example, various photosensitive polymers such as those disclosed in JP-A-60-22903, which are exposed and cured before laminating a photosensitive resin layer, JP-A-62-507.
The epoxy resin disclosed in JP-A-60 is heat-cured, the gelatin disclosed in JP-A-63-133151 is hardened, and further JP-A-3-2.
The one using the urethane resin and the silane coupling agent disclosed in JP-A-99653, JP-A-3-27324.
Examples thereof include those using the urethane resin disclosed in JP-A-8. In addition, those obtained by hardening gelatin or casein are also effective. Further, for the purpose of softening the primer layer, polyurethane, polyamide, styrene / butadiene rubber, carboxy-modified styrene / butadiene rubber, acrylonitrile / butadiene rubber, carboxy-modified acrylonitrile having a glass transition temperature of room temperature or lower is contained in the primer layer. Polymers such as / butadiene rubber, polyisoprene, acrylate rubber, polyethylene, chlorinated polyethylene and chlorinated polypropylene may be added. The addition ratio is arbitrary,
The primer layer may be formed only by the additive as long as the film layer can be formed. In addition, in accordance with the above-mentioned purpose, these primer layers have a dye, a pH indicator, a printout agent, a photopolymerization initiator, an adhesion aid (for example, a polymerizable monomer, a diazo resin, a silane coupling agent, a titanate coupling agent). Agents, aluminum coupling agents), pigments, and additives such as silica powder and titanium oxide powder. After the application, it can be cured by exposure. Generally, the coating amount of the primer layer is suitably in the range of 0.1 to 20 g / m ² as dry weight, preferably 1 to 10 g / m ² , and more preferably 1 to 5 g.
/ M ² .

The photopolymerizable photosensitive layer used in the present invention has at least the following three components, namely, (1) a monomer having at least one photopolymerizable ethylenically unsaturated group,
It contains an oligomer or a macromonomer, (2) a polymer compound having film-forming ability, and (3) a photopolymerization initiator. Component (1): at least one photopolymerizable ethylenic
Monomers, oligomers or macromolecules containing unsaturated groups
The monomer that can be used to Nomar present invention, the oligomers or macromers, for example, (A) alcohols (e.g., ethanol, propanol, hexanol, 2-ethylhexanol, cyclohexanol, glycerin, hexanediol, trimethylolpropane, Acrylic acid or methacrylic acid ester of pentaerythritol, sorbitol, triethylene glycol, polyethylene glycol, polypropylene glycol, ω-methoxy polyethylene glycol, etc. (B)
Amines (eg, ethylamine, butylamine, benzylamine, ethylenediamine, hexamethylenediamine, diethylenetriamine, xylylenediamine, ethanolamine, aniline, etc.) and glycidyl acrylate,
With a reaction product with glycidyl methacrylate or allyl glycidyl, (C) carboxylic acids (for example, acetic acid, propionic acid, benzoic acid, acrylic acid, methacrylic acid, succinic acid, maleic acid, phthalic acid, tartaric acid, citric acid, etc.) Reaction products with glycidyl acrylate, glycidyl methacrylate or allyl glycidyl, (D) amide derivatives (eg, acrylamide, N-methylol acrylamide, t-butyl acrylamide, methylene bis acrylamide, diacetone acrylamide, etc.) and the like. You can

Further, urethane acrylates such as those described in JP-B-48-41708, JP-B-50-6034 and JP-A-51-37193, JP-A-SHO-4.
Polyfunctional acrylates such as polyester acrylates described in 8-64183, JP-B-49-43191 and JP-B-52-30490, and epoxy acrylates obtained by reacting an epoxy resin with (meth) acrylic acid, Methacrylate, US Pat. No. 4,540,64
N-methylol acrylamide derivatives described in No. 9 can be mentioned. Furthermore, Japan Adhesives Association magazine Vo
l.20, No. 7, pp. 300-308 (1984)
Those described as photocurable monomers and oligomers in P. Dreyfuss & RP Quirk, Encycl. Pol.
ym. Sci. Eng., 7, 551 (1987), Chemical Industry, 38, 56
(1987), Polymer Processing, 35,262 (1986).
The macromer monomers described in et al. Can also be used. However, the unsaturated group may be present in a mixture of acryl, methacryl, allyl, vinyl groups and the like, without being limited thereto. In addition, these may be used alone or in combination.

Examples of useful monomers used in the present invention include the following.

[0010]

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[0011]

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[0012]

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The amount used is 5% by weight to 80% by weight, preferably 20% by weight to 70% by weight, based on the total solid content of the photopolymerizable photosensitive layer.

Component (2): High content having film forming ability
Sub-Compounds As the polymer compound having film-forming ability used in the present invention, the following polymers and copolymers can be used. (1) Vinyl polymers such as polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl methyl ether, polyvinyl chloride, polyethylene and the like, and copolymers thereof. (2) (Meth) acrylic acid ester polymers and alkyl (meth) acrylamide polymers such as ethyl poly (meth) acrylate, butyl poly (meth) acrylate, allyl poly (meth) acrylate, poly t-butyl acrylamide, polydi Acetone acrylamide and the like, and copolymers thereof. (3) Unvulcanized rubber, for example natural rubber, polybutadiene,
Polyisobutylene, polyneoprene, etc., and copolymers thereof. (4) Polyethers such as polyethylene oxide and polypropylene oxide.

(5) Polyamide, a copolymer of the following monomers, for example, caprolactam, laurolactam, hexamethylenediamine, 4,4'-bis-aminocyclohexylmethane, 2,4,4-trimethylhexamethylenediamine, isophorone. Diamine, diglycols, isophthalic acid, adipic acid, sebacic acid, etc. (6) Polyester, for example, a condensate of terephthalic acid, adipic acid and the like with ethylene glycol, 1,4-butanediol and the like. (7) Polyurethane, such as hexamethylene diisocyanate, toluene diisocyanate, naphthalene-1,
Polyurethane of 5-diisocyanate, isophorone diisocyanate, etc. and ethylene glycol, 1,4-butanediol, polyester. Further, isophoronediamine, hexamethylenediamine, or the like may be used as the chain extender. Further, as the polymer compound capable of forming a film, a polymer compound having a photopolymerizable or photocrosslinkable olefinic unsaturated double bond group in a side chain can be used, but the polymer compound is not limited thereto. Not a thing. Also,
These may be used alone or in combination. The amount used is 20 based on the total solid content of the photosensitive layer.
% To 90% by weight, preferably 30% to 80% by weight, more preferably 35% to 70% by weight.

Component (3): Photopolymerization initiator system As the photopolymerization initiator used in the present invention, a photopolymerization initiator or two or more kinds of photopolymerization known in patents, literatures and the like are selected depending on the wavelength of the light source used. A combination system of initiators can be appropriately selected and used. The following are typical examples of the photopolymerization initiator system, but the photopolymerization initiator system is not limited thereto. For example, US Pat.
Certain photosensitive dyes described in 850,445, complex initiation system of dye and amine (JP-B-44-20189), combination system of hexaarylbiimidazole, radical generator and dye (JP-B-45-37377) , Hexaarylbiimidazole and p-
System of dialkylaminobenzylidene ketone (Japanese Patent Publication No. 47-2
528, JP-A-54-155292), a system of a cyclic cis-α-dicarbonyl compound and a dye (JP-A-48-84183), a system of a cyclic triazine and a merocyanine dye (JP-A-54-151024).
No.), 3-ketocoumarin and activator system (JP-A-52-11268)
1, JP-A-58-15503), biimidazole, styrene derivative, thiol system (JP-A-59-140203), organic peroxide and dye system (JP-A-59-140203, JP-A-59-140203). Sho 59-189
340), a system of a rhodanine skeleton dye and a radical generator (JP-A-2-244050), a system of titanocene and 3-ketocoumarin dye (JP-A-63-221110), a titanocene and xanthene dye and further an amino group or urethane. A system in which an addition-polymerizable ethylenically unsaturated compound containing a group is combined (JP-A-4-221958, JP-A-4-219756), a system of titanocene and a specific merocyanine dye (JP-A-6-295061), etc. I can give you.

In the photopolymerization initiation system of the present invention, the known 4
A dye or pigment having a λmax of 00 nm or more is made to coexist. Examples of preferred dyes or pigments are polynuclear aromatics
(Eg, pyrene, perylene, triphenylene, etc.), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal, etc.), cyanines (eg, thiacarbocyanine, oxycarbocyanine, etc.), merocyanines ( For example, merocyanine,
Carbomerocyanine etc.), thiazines (eg thionine, methylene blue, toluidine blue etc.), acridines (eg acridine orange, chloroflavin,
Acriflavine, etc.), phthalocyanines (eg, phthalocyanine, metal phthalocyanine, etc.), porphyrins (eg, tetraphenylporphyrin, metalporphyrin, etc.), chlorophylls (eg, chlorophyll, chlorophyllin, central metal substituted chlorophyll, etc.),
Anthraquinones (for example, anthraquinone etc.), squarylium (for example, squarylium etc.), etc. are mentioned.

More preferably, Japanese Examined Patent Publication No. 37-13034
Styryl dyes described in JP-A-62-143044, cation dyes described in JP-A-62-143044, quinoxalinium salts described in JP-B-59-24147, new methylene blue compounds described in JP-A-64-33101, and JP-A-64-59767. Anthraquinones described in JP-A No. 2-1714, benzoxanthenes described in JP-A No. 2-1714, JP-A No. 22614/1990, and JP-A No.
No. 226149, acridines, Japanese Examined Patent Publication No. 40-2
Pyrylium salts described in 8499, Japanese Examined Patent Publication No. 46-423
No. 63, cyanines, benzofuran dyes described in JP-A-2-63053, conjugated ketone dyes described in JP-A-2-85858, JP-A-2-216154, JP-A-57.
No. 10605, Azocinnamylidene derivatives described in JP-B No. 2-30321, JP-A-1-28710.
Cyanine dyes described in JP-A No. 62-31844,
JP-A-62-31848, JP-A-62-143043
Xanthene dyes described in JP-B No. 59-28325, amino styryl ketones described in JP-B No. 59-28325, and JP-B No. 61-9621.
JP-A-2-179643, JP-A-2-24405
No. 0, JP-B-59-28326, JP-A-59-893.
No. 03, Japanese Patent Application No. 6-269047, and other merocyanine dyes. More preferable examples are described in Japanese Patent Publication No. 61-9621, Japanese Patent Publication No. 2-179643, Japanese Patent Publication No. 2244050, Japanese Patent Publication No. 59-28623, Japanese Patent Publication No. 59-89303, and Japanese Patent Application No. 6-269047. The merocyanine dyes of These may be used alone or in combination of two or more. The amount of the photopolymerization initiator system added is 0.1 to 25% by weight, preferably 3 to 20% by weight, based on the total solid content of the photosensitive layer.

It is preferable to add a thermal polymerization inhibitor in addition to the above other components , for example, hydroquinone, p-methoxyphenol,
Di-t-butyl-p-cresol, pyrogallol, t-
Butylcatechol, 4,4'-thiobis (3-methyl-
6-t-butylphenol), 2,2′-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole, etc. are useful, and in some cases, dyes or pigments and pigments for the purpose of coloring the photosensitive layer and A pH indicator or a leuco dye may be added as a printing agent. A silicone-based surfactant or a fluorine-based surfactant may be added to improve coatability. Further, a diazo resin may be added to improve the adhesion between the photosensitive layer and the primer layer. Further, in order to improve the adhesion between the silicone rubber layer and the photosensitive layer, a small amount of polydimethylsiloxane, methylstyrene-modified polydimethylsiloxane, olefin-modified polydimethylsiloxane, polyether-modified polydimethylsiloxane, silane coupling agent in the photosensitive layer. Silicone compounds such as silicone diacrylate and silicone dimethacrylate may be added. In addition, a plasticizer (for example, polyethylene glycol, tricresyl phosphate, etc.) and a stabilizer (for example, phosphoric acid) for imparting flexibility to the coating film may be added. The amount of these additives added is usually 10% by weight or less based on the total solid content of all the photosensitive layers. In some cases, a hydrophobic silica powder treated with a silane coupling agent containing a (meth) acryloyl group or an allyl group may be added in an amount of 50% by weight or less based on the total solid content of all photosensitive layers.

The above-mentioned photosensitive layer composition used in the present invention is, for example, 2-methoxyethanol, 2-methoxyethyl acetate, propylene glycol methyl ethyl acetate, methyl lactate, ethyl lactate, propylene glycol monomethyl ether, ethanol, methyl ethyl ketone,
A suitable solvent such as N, N-dimethylacetamide or the like is dissolved alone or in a mixed solvent thereof, and the solution is coated on the substrate.
The coating weight is suitably in the range of 0.1 to 20 g / m ² after drying, preferably in the range of 0.5 to 10 g / m ² .

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) Diorganopolysiloxane (number average molecular weight is 3,000 to 40,000) 100 parts by weight (b) Condensation type crosslinking agent 3 to 70 parts by weight (c) Catalyst 0.01 to 40 parts by weight The diorganopolysiloxane of the component (a) is a polymer having a repeating unit represented by the following general formula, R ₁ and R ₂ are an alkyl group having 1 to 10 carbon atoms, a vinyl group or an aryl group, and It may have other suitable substituents. Generally 60 for R ₁ and R ₂
Those in which% or more is a methyl group, a vinyl halide group, a halogenated phenyl group or the like are preferable. —Si (R ₁ R ₂ ) O— It is preferable to use a diorganopolysiloxane having hydroxyl groups at both ends. Further, the component (a) has a number average molecular weight of 3,000 to 40,000, and more preferably 5,000 to 36,000.

The component (b) may be of any condensation type, but is preferably one represented by the following general formula. R ₁ m · Si · Xn (m + n = 4, n is 2 or more) where R ₁ has the same meaning as R ₁ described above, and X
Is halogen such as Cl, Br, I; H, OH; OCO
_{R 3, OR 3, -O-} N = CR 4 R 5, an organic substituent such as -NR ₄ R _5. Here, R ₃ is an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 20 carbon atoms, R ₄ ,
R ₅ represents an alkyl group having 1 to 10 carbon atoms. Component (c)
Examples thereof include metal carboxylates of tin, zinc, lead, calcium, manganese, etc., such as dibutyl laurate, lead octylate, lead naphthenate, and known catalysts such as chloroplatinic acid.

Composition B (d) Diorganopolysiloxane having an addition-reactive functional group (number average molecular weight of 3,000 to 40,000) 100 parts by weight (e) Organohydrogenpolysiloxane 0.1 to 10 parts by weight Part (f) Addition catalyst 0.00001 to 1 part by weight The diorganopolysiloxane having an addition-reactive functional group of the component (d) is an alkenyl group directly bonded to a silicon atom in one molecule (more preferably vinyl). Organopolysiloxane having at least two groups), the alkenyl group may be at the terminal or intermediate molecular weight, and as the organic group other than the alkenyl group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, aryl Groups. Component (d) may optionally have a trace amount of hydroxyl groups. The number average molecular weight of the component (d) is 3,000 to 40,0.
00, and more preferably 5,000 to 36,000
0.

As component (e), polydimethylsiloxane having hydrogen groups at both ends, α, ω-dimethylpolysiloxane, (methylsiloxane) (dimethylsiloxane) copolymer having methyl groups at both ends, cyclic polymethylsiloxane, both Examples include polymethylsiloxane having a terminal trimethylsilyl group, dimethylsiloxane having both terminal trimethylsilyl groups (methylsiloxane) copolymer, and the like. 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 speed of these compositions, vinyl group-containing organopolysiloxane such as tetracyclo (methylvinyl) siloxane, carbon-carbon triple bond-containing alcohol, acetone, methyl ethyl ketone, methanol, ethanol, propylene glycol monomethyl ether. It is also possible to add a crosslinking inhibitor such as. The silicone rubber layer may contain, if necessary, fine powder of an inorganic substance such as silica, calcium carbonate, or titanium oxide, an adhesion aid such as a silane coupling agent, a titanate coupling agent, or an aluminum coupling agent, or photopolymerization. An initiator may be added.

If the thickness of the silicone rubber layer in the present invention is small, there is a problem that the ink repulsion property is lowered and scratches easily occur, and if the thickness is large, the developability is deteriorated. preferably 0.5 to 5 g / m ² as, more preferably 1 to 3 g / m ^2. In the waterless planographic printing plate described here, various silicone rubber layers may be further coated on the silicone rubber layer. In addition, an adhesive layer is provided between the photosensitive layer and the silicone rubber layer for the purpose of increasing the adhesive force between the photosensitive layer and the silicone rubber layer or preventing poisoning of the catalyst in the silicone rubber layer composition. May be. Furthermore, in order to protect the surface of the silicone rubber layer, a transparent film on the silicone rubber layer,
For example, polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyethylene terephthalate, cellophane, etc. may be laminated or coated with a polymer. These films may be used after being stretched. Further, the surface may be matted, but the one without matting is preferable in the present invention.

The waterless planographic printing plate thus obtained was Ar
After direct exposure with a visible light laser such as a laser or a YAG-SHG laser, development processing is performed. In the present invention, a post-heating step may be provided before the development treatment in order to increase the polymerization efficiency of the photopolymerizable photosensitive layer. The heating temperature / time is 60 ° C to 150 ° C, 10 seconds to 10 minutes, preferably 80 ° C to 140 ° C, 15 seconds to 5 minutes, more preferably 100 ° C to 130 ° C, 15 seconds to 5 minutes.

As the developing solution used in the present invention, those known as a developing solution for a waterless planographic printing 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 used. 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 or the like) to which the following polar solvent is added, or a 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, polypropylene glycol, tetraethylene glycol, etc.) Ketones (acetone, methyl ethyl ketone, etc.), esters (ethyl acetate, methyl lactate, butyl lactate,
Propylene glycol monomethyl ether acetate,
Diethylene glycol acetate, diethyl phthalate, etc.) Others (triethyl phosphate, tricresyl phosphate, etc.)

Further, water is added to the organic solvent-based developer, or the organic solvent is solubilized in water by using a surfactant or the like, and an alkaline agent (for example, sodium carbonate or diethanolamine) is further added. , Sodium hydroxide, etc.)
And water (tap water, pure water, distilled water, etc.) and the like. Further, dyes such as crystal violet, Victoria Pure Blue, and Astrazone Red can be added to the developing solution to dye the image area simultaneously with the development. 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 temperature of the developer is arbitrary, but preferably 1
0 ° C to 50 ° C. As a result, the ink repellent layer in the image area is removed, and that area becomes the ink receiving area.

In the printing plate thus obtained, the exposed image portion can be dyed with a dyeing solution so as to be detected in order to confirm the image forming property. When the developer does not contain a dye for dyeing the exposed image area, it is treated with a dyeing solution after development. By soaking the dyeing solution in a soft pad and rubbing the image area lightly, only the exposed image area of the photosensitive layer is dyed, whereby it can be confirmed that the development is sufficiently performed up to the highlight area. As the dyeing solution, one or more selected from water-soluble disperse dyes, acid dyes and basic dyes can be used alone or in a mixture of two or more of water, alcohols, ketones and ethers. What is dissolved or dispersed is used. In order to improve the dyeability, carboxylic acids, amines, surfactants,
It is also effective to add a dyeing aid, an antifoaming agent and the like. The printing plate dyed with the dyeing solution is preferably washed with water and then dried, whereby the stickiness of the plate surface can be suppressed and the handleability of the printing plate can be improved. Further, when the printing plates thus treated are stacked and stored, it is preferable to insert and sandwich a slip sheet for protecting the printing plates. It is preferable to perform the above-mentioned developing treatment and dyeing treatment, or subsequent washing with water and drying treatment with an automatic processor. A preferable example of such an automatic processor is described in JP-A-2-220061.

[0030]

Since the waterless planographic printing plate has high sensitivity in the visible light region, practical writing with a visible light laser becomes possible.

[0031]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples. Examples 1 to 8 and Comparative Examples 1 to 3 (Preparation of support) A rolled aluminum plate having a thickness of 0.24 mm was first immersed in a 10 wt% sodium hydroxide aqueous solution at 50 ° C.
After dipping for 60 seconds in a cleansing treatment, it was washed with water and then neutralized with a 20 wt% nitric acid aqueous solution. After washing with water, 0.7
In a weight% nitric acid aqueous solution, a rectangular wave alternating waveform having an anode voltage of 13 V and a cathode voltage of 6 V was used (Japanese Patent Laid-Open No. 52-
Power supply waveform described in the embodiment of Japanese Patent Publication No. 77702) 2
It was electrochemically grained for 0 seconds. Then 25% by weight
2.5 degree etching at 55 ℃ in sodium hydroxide solution
After adjusting the processing time so that it becomes g / m ² ,
It was washed with water and neutralized with a 20 wt% nitric acid aqueous solution. After washing with water, the amount of oxide film is 1.7g / m in 18% by weight sulfuric acid aqueous solution.
At ^2, anodized at 25 ° C. Current density 1.5A / dm ^2, then washed with water, immersed for 1 minute at 70 ° C. in 2 wt% aqueous sodium silicate solution, washed with water, and dried to obtain a support.
The average roughness of the surface of the obtained support was 0.4 μm (Ra indication).

(Application of Primer Layer) The following primer layer was applied on the support so that the dry weight was 3 g / m ^2, and the coating was dried by heating at 130 ° C. for 2 minutes. Polyurethane resin [isophorone diisocyanate / polyester (adipic acid / 1,4-butanediol / 2,2-dimethylpropan-1,3-diol) / isophoronediamine] 10 parts by weight p-diazodiphenylamine and paraformaldehyde Hexafluorophosphate of condensation polymer 0.1 parts by weight MCF323 (Dainippon Ink and Chemicals, Inc., surfactant) 0.03 parts by weight Propylene glycol methyl ether acetate 50 parts by weight Methyl lactate 20 parts by weight Part ・ Pure water 1 part by weight After that, Nuark FT261V UDNS ULTRA-PLUS FLIPTO
20 count exposure was performed using a P PLATE MAKER vacuum exposure machine.

(Coating of Photosensitive Layer) A photopolymerizable photosensitive liquid having the following composition was coated on the primer layer so as to have a dry weight of 3 g / m ^2, and dried at 100 ° C. for 1 minute. Polyurethane resin [isophorone diisocyanate / polyester (adipic acid / 1,4-butanediol / 2,2-dimethylpropan-1,3-diol) / isophoronediamine] 1.5 parts by weight pentaerythritol tetraacrylate 0.3 Part by weight: 1 mol of xylylenediamine / 1 mol of glycidyl methacrylate (polyfunctional monomer) 1.2 parts by weight Photopolymerization initiator system shown in Table 1 MCF323 (Dainippon Ink and Chemicals, Inc., interface) Activator) 0.03 parts by weight Methyl ethyl ketone 10 parts by weight Propylene glycol monomethyl ether 25 parts by weight

(Application of Ink Repellent Layer) The following silicone rubber composition liquid was dried on the above photopolymerizable photosensitive layer in a dry weight of 2 g /
It was coated so as to have a surface area of m ² and dried at 140 ° C. for 2 minutes.・ Α, ω-Divinylpolydimethylsiloxane (Polymerization degree approx. 700) 9 parts by weight ・ (CH ₃ ) ₃ -Si-O- (SiH (CH ₃ ) -O) ₈ -Si (CH ₃ ) ₃ 0.5 parts by weight parts polydimethylsiloxane (polymerization degree about 8,000) 0.5 parts by weight olefin - chloroplatinic acid 0.2 parts by weight inhibitor _{[CH≡CC (CH 3) 2 Si} (CH 3) 3] 0.3 weight Parts-ISOPAR G (manufactured by Esso Kagaku Co., Ltd.) 140 parts by weight A 6 μm thick polyethylene terephthalate film was laminated on the surface of the silicone rubber layer obtained as described above to obtain a waterless planographic printing plate.

The photosensitivity test was conducted with visible light (sensitivity evaluation) and Ar laser light (wavelength = 488 nm) (tone reproducibility evaluation).
Of each monochromatic light. As visible light, a tungsten lamp is used as a light source, and a Kenko optical filter BP-4 is used.
Monochromatic light obtained through 9 was used. Fuji PS for sensitivity measurement
A step guide (manufactured by Fuji Photo Film Co., Ltd., a step tablet in which the transmission optical density of the first stage is 0.05 and sequentially increases by 0.15 up to 15 stages) was used. The number of clear steps of the PS step guide (the number of steps where the silicone rubber layer completely remains after development) when exposed for 15 seconds at an illuminance of 0.0132 mW / cm ² on the photosensitive film surface is shown in Table 1. The larger this value is, the higher the sensitivity is. The tone reproducibility was evaluated by using an image setter XL manufactured by Optronics Co., Ltd. so that the surface amount of the photosensitive material was 0.1 mJ / cm ² by Ar laser light, and image exposure (4000 dpi) was performed. The area (unit:%) of reproducible highlight and shadow halftone dots (corresponding to 175 lines / inch) was evaluated. The smaller the numerical value of highlight reproducibility and the larger the numerical value of shadow reproducibility, the better the tone reproducibility. afterwards,
The laminate film was peeled off by heating at 100 ° C. for 1 minute, and the following developing treatment was carried out immediately.

(Development treatment) The plate was dipped in polypropylene glycol at 35 ° C. for 30 seconds and then rubbed with a development pad while washing with water to remove the silicone rubber layer in the unexposed area. Then, dye with a dyeing solution of the following composition,
The sensitivity and tone reproducibility were evaluated. (Staining solution) -Crystal violet 0.1 part by weight-Diethylene glycol monoethyl ether 15 parts by weight-Pure water 85 parts by weight

Table 1 shows the sensitivity (the number of steps of the step guide in which the photosensitive layer remains completely after development) and the tone reproducibility. From Table 1, the waterless planographic printing plate of the present invention has a thickness of 400 nm.
It can be seen that the sensitivity is obviously higher than that of the waterless planographic printing plate of Comparative Example which does not contain the compound having the above λ max, and the tone reproducibility is good.

[0038]

[Table 1] Table 1 Sample Photopolymerization initiator system Sensitivity Reproducibility (%) Species amount Highlight Shadow Example 1 Sensitizing dye (1) 0.2 parts by weight 7 2 98 Initiator (1) 0.3 Parts by weight Sensitizing dye (2) 0.15 parts by weight Example 2 Initiator (1) 0.2 parts by weight 8 298 Initiator (2) 0.3 parts by weight Sensitizing dye (1) 0.2 parts by weight Example 3 Initiator (1) 0.2 parts by weight 7 298 Initiator (2) 0.2 parts by weight Sensitizing dye (2) 0.15 parts by weight Example 4 Initiator (2) 0.2 parts by weight 7 298 Initiator (3) 0.3 parts by weight Example 5 Sensitizing Dye (3) 0.2 parts by weight 7 298 Initiator (4) 0.3 parts by weight Example 6 Sensitizing Dye (4) 0 0.3 parts by weight 8 2 98 Initiator (5) 0.3 parts by weight Example 7 Sensitizing dye (5) 0.2 parts by weight 7 2 98 Initiator (6) 0.3 parts by weight Example 8 Sensitizing dye (6) 0.2 parts by weight 7 298 Initiator (7) 0.3 parts by weight Parts Comparative Example 1 Initiator (8) 0.4 parts by weight Silicone rubber layer entire surface separation initiator (9) 0.1 parts by weight Comparative Example 2 Initiator (1) 0.3 parts by weight Silicone rubber layer entire surface separation Comparative Example 3 Initiator (2) 0.2 parts by weight Silicone rubber layer entire surface peeling initiator (3) 0.3 parts by weight

The structural formulas of the sensitizing dyes (1) to (6) and the values of λmax and the structural formulas of the initiators (1) to (9) used in the above Examples and Comparative Examples are shown below.

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[0041]

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[0042]

[Chemical 6]

[0043]

[Chemical 7]

[0044]

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Claims (1)

[Claims] 1. A primer layer, a photopolymerizable photosensitive layer and a silicone rubber layer are laminated in this order on a support,
A photosensitive lithographic printing plate requiring no fountain solution characterized in that the photopolymerizable photosensitive layer contains at least one compound having a λmax of 400 nm or more is exposed using a visible light laser as a light source. A method for producing a lithographic printing plate that does not require fountain solution.