JPH06214403A - Dyeing liquid for waterless planographic printing plate and plate making method - Google Patents

Abstract

PURPOSE:To improve the flaw resistance of a plate surface after plate making and to improve developability by incorporating a specific compd., water, surfac tant and dyes into this dyeing liquid. CONSTITUTION:The dyeing liquid to be used for the waterless planographic printing plate constituted by successively laminating a photosensitive layer and a silicone rubber layer on a substrate contains the compd. expressed by formula, the water, the surfactant and the dyes. In the formula, R<3> and R<4> denote respectively the same or different substd. or unsubstd. alkyl group, phenyl group or aralkyl group; R<2> denotes a hydrogen atom, substd. or unsubstd. alkyl group; R<5> denotes a hydrogen atom, hydroxyl group or substd. or unsubstd. alkyl group; (m) and (n) are >=1 integer. The waterless planographic printing plate constituted by successively laminating the photosensitive layer and the silicone rubber layer on the substrate is subjected to image exposing and is then developed by a developer substantially consisting of the water alone. The photosensitive layer and/or primer layer exposed by the removal of the silicon rubber is selectively dyed by using the dyeing liquid, by which the plate making is executed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a waterless lithographic printing plate dyeing solution, and more particularly to a waterless lithographic printing plate dyeing solution which can improve scratch resistance of a plate surface after plate making, and a waterless lithographic plate using the same. The present invention relates to a printing plate making method.

[0002]

2. Description of the Related Art Conventionally, as a method for dyeing an image area of a waterless photosensitive lithographic printing plate after development, Japanese Patent Publication No. 61-53716.
As described in the publication, a method is known in which a plate surface is rubbed with a pad impregnated with a solution of a water-soluble disperse dye, an acid dye or a basic dye, which has a property of dyeing an exposed image area. ing. By carrying out such a treatment, it is possible to confirm that the development has been completed, and it becomes clear at a glance whether or not there are scratches on the silicone rubber layer, pinhole-like defects, and the like. Furthermore, by using a plate image area reader, it is possible to check the proper ink supply amount during printing. On the other hand, various types of waterless lithographic printing plates using silicone rubber as an ink repellent layer have been proposed, for example, Japanese Patent Publication No. 44-23042.
Issue, Japanese Examined Patent Publication No. 46-16044, Japanese Examined Patent Publication No. 51-1708
1, JP-B-54-26923, JP-A-56-800.
No. 64, Japanese Patent Publication No. 55-22781, Japanese Patent Publication No. 54-26
Waterless lithographic printing plates disclosed in Japanese Patent Publication No. 923, Japanese Patent Publication No. 56-23150, and the like. Since such a waterless lithographic printing plate has a soft silicone rubber as a non-image area, it is easily scratched depending on how to handle it until it is mounted on a printing machine after plate making, and may be damaged by paper dust during printing. If the silicone rubber is damaged, the ink-philic photosensitive layer, the primer layer, or the surface of the substrate is exposed, and as a result, the ink is transferred to the non-image area of the printed matter in a scratched pattern, resulting in contamination. In order to avoid such stains, it is necessary to make the silicone rubber layer less likely to be scratched, but increasing the curing degree of the silicone rubber layer deteriorates the developability, so it is a good idea to strengthen the silicone rubber layer itself to a certain extent or more. Absent. Therefore, a method of softening the lower layer of the silicone rubber layer and diffusing the external force applied to the surface of the silicone rubber layer is usually selected. However, if a plasticizer is added or the structure of the binder is changed in order to soften the photosensitive layer or the primer layer, which is the lower layer of the silicone rubber, the developability deteriorates to a greater or lesser extent. In the method of softening the photosensitive layer or primer layer by immersing the plate in a liquid containing a plasticizer or an organic solvent before development, the photosensitive layer in the image area and the non-image area may be swollen or dissolved during development. No clear difference appears, and as a result, developability deteriorates.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a dyeing solution which overcomes the above-mentioned drawbacks of the prior art and improves the scratch resistance of the silicone rubber layer in the non-image area. Another object of the present invention is to provide a method for making a waterless planographic printing plate using this dyeing solution.

[0004]

The present inventors have completed the present invention as a result of intensive studies to solve the above problems. That is, the present invention is a dyeing solution for a waterless lithographic printing plate, which comprises a photosensitive layer and a silicone rubber layer laminated in this order on a substrate, and contains a compound represented by formula (1), water, a surfactant and a dye. A dyeing solution for a waterless lithographic printing plate is provided. R ¹ -CO-O-CH ₂ -[-C (R ² ) (-O-CO-R ⁴ )-] _m -[-CH (R ⁵ )-] _n -O-CO-R ³ (1) (Wherein R ¹ , R ³ and R ⁴ are the same or different and each represent a substituted or unsubstituted alkyl group, a phenyl group or an aralkyl group, and R ² represents a hydrogen atom, a substituted or unsubstituted alkyl group, R ⁵ is a hydrogen atom, a hydroxyl group, or
A substituted or unsubstituted alkyl group is shown. Also, m and n
Is an integer of 1 or more. ) Further, in the present invention, a waterless photosensitive lithographic printing plate obtained by laminating a photosensitive layer and a silicone rubber layer on a substrate in order is subjected to imagewise exposure and then developed with a developer consisting essentially of water to remove the silicone rubber. The present invention provides a plate making method for a waterless planographic printing plate, which comprises selectively dyeing the exposed photosensitive layer and / or primer layer with the dyeing solution.

The contents of the present invention will be further described in detail. As the developer used in the plate making method of the waterless planographic printing plate of the invention, water, an organic solvent, or an aqueous solution of an organic solvent can be used. Examples of the organic solvent include diisobutyl ketone, methyl ethyl ketone, methyl isobutyl ketone, acetone, acetophenone, isophorone, diethyl succinate, methyl benzoate, diethyl oxalate,
Dimethyl phthalate, isobutyl acetate, benzyl benzoate, ethyl acetate, propyl acetate, butyl acetate, amyl acetate, hexyl acetate, methyl butyrate, ethyl butyrate, propyl butyrate, ethyl cellosolve acetate, ethylene glycol, ethylene glycol mono-phenyl ether, Ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol diacetate, ethylene glycol benzyl ether, ethylene glycol mono-
n-pentyl ether, ethylene glycol-mono-n
-Hexyl ether, ethylene glycol-mono-n-
Heptyl ether, ethylene glycol mono-n-octyl ether, diethylene glycol, diethylene glycol di-n-butyl ether, diethylene glycol diacetate, diethylene glycol mono-acetate, diethylene glycol mono-n-pentyl ether, diethylene glycol mono-n-hexyl ether, Diethylene glycol-mono-n-heptyl ether, diethylene glycol-mono-octyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, polypropylene glycol, triethylene glycol, tetraethylene glycol, polyethylene Recall,

Triethylene glycol dimethyl ether, triethylene glycol monomethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol dimethyl ether, ethyl ether, dioxane, tetrahydrofuran, n-amyl alcohol, benzyl alcohol , Cyclohexanone, cyclohexanol, N-
Benzylethanolamine, anisyl alcohol, dimethylbenzylcarbitol, 2-N-ethylanilinoethanol, propylene glycol monophenyl ether, N-phenylethanolamine, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec- Butanol, t-butanol, 3-methoxybutanol, furfuryl alcohol, tetrahydrofurfuryl alcohol, 1,2-propylene oxide, ethyl cellosolve, butyl cellosolve, pentane,
Hexane, heptane, octane, nonane, decane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, gasoline, kerosene, light oil, heavy oil, Isopar G, Isopar H, Exol D100, Exol D110 (Exxon Chemical), toluene , Xylene, formic acid, acetic acid, propanoic acid, butyric acid, acrylic acid, propiolic acid, caproic acid, cyclopropanecarboxylic acid, benzoic acid, 2-aminopropanoic acid, succinic acid, phthalic acid, maleic acid, fumaric acid, tartaric acid, shu Acid, acetoacetic acid, malonic acid, citric acid, etc. are used.

Among these, one kind or two or more kinds can be used in combination, but an organic solvent which is hardly soluble in water is combined with an easily soluble organic solvent to form a uniform aqueous solution or a solvent which can swell silicone rubber. To control the developing power in combination with a solvent that does not swell, or to combine a volatile organic solvent with a non-volatile organic solvent to control the variation of the liquid composition, or to add a photosensitive layer-soluble organic solvent to the photosensitive layer insoluble The developing power can be controlled in combination with an organic solvent, or a plurality of solvents can be simultaneously selected depending on the purpose. The most preferable developer for a waterless lithographic printing plate is a developer consisting essentially of water. Further, surfactants, antifoaming agents, acids, bases, chelating agents, preservatives and the like can also be used.

The surfactant to be used has the purpose of controlling the solubility of the solvent in the developing solution to control the penetration amount of the solvent into the waterless lithographic printing plate, the purpose of solubilizing the solvent in water, and imparting the developing ability. Since it is selected according to various purposes such as the purpose, there is no limitation according to the kind of the surfactant.For such purpose, for example, nonionic surfactants include polyoxyalkylene alkyl ether and polyoxyalkylene alkyl. Phenyl ethers (eg, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene Renoctyl phenyl ether, polyoxyethylene nonyl phenyl ether, etc.), oxyethylene / oxypropylene block copolymer, polyethylene glycol, sorbitan fatty acid esters (eg, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan tristearate) Rate, sorbitan monooleate, sorbitan trioleate, sorbitan sesquioleate, sorbitan distearate, etc.), polyoxyethylene sorbitan fatty acid esters (eg, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, poly Oxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene so Bitan monooleate, polyoxyethylene sorbitan trioleate, etc.), polyoxyethylene sorbitol fatty acid esters (tetraoleic acid polyoxyethylene sorbit, etc.), glycerin fatty acid esters (eg, glycerol monostearate, glycerol monooleate, etc.) , Polyoxyethylene fatty acid esters (for example,
Polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, etc.), polyoxyethylene alkylamines, polyoxyethylene hydrogenated castor oil, alkylalkanolamides,

As the anionic surfactant, fatty acid salts (for example, mixed fatty acid soda soap, semi-hardened tallow fatty acid sodium soap, sodium stearate soap, semi-hardened tallow fatty acid potassium soap, oleic acid potassium soap, castor oil potassium soap, etc.), Alkyl sulfate ester salts (eg sodium lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate etc.), alkylbenzene sulfonates (eg sodium dodecylbenzene sulfonate etc.), alkylnaphthalene sulfonates (eg sodium alkylnaphthalene sulfonate) Etc.), alkyl sulfosuccinates (eg sodium dialkyl sulfosuccinate), alkyl diphenyl ether disulphonates (eg alkyl diphenyl ether disulfate) Sodium phosphate, etc., alkyl phosphates, polyoxyethylene alkyl (alkylaryl) sulfate ester salts, naphthalene sulfonic acid formalin condensates, polyoxyethylene alkyl phosphate esters, cationic and amphoteric surfactants , Alkylamine salts (eg, coconut amine acetate, stearyl amine acetate, coconut amine hydrochloride, stearyl amine hydrochloride, etc.), quaternary ammonium salts (eg, lauryl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, cetyl trimethyl ammonium) Chloride, distearyl dimethyl ammonium chloride, alkylbenzyl dimethyl ammonium chloride, etc., alkyl betaines (eg, lauryl betaine, suture) Allyl betaine), amine oxides (e.g., lauryl dimethyl amine oxide and the like), lauryl carboxymethyl hydroxyethyl imidazolium betaine. Among these, 1 type (s) or 2 or more types can be used together.

Since the defoaming agent is selected for the purpose of suppressing foaming of the developing solution, various defoaming agents can be selected depending on the properties of the developing solution, and the silicone defoaming agent is particularly excellent. Examples of the silicone defoaming agent preferably used here include dimethyl silicone oil (viscosity 10 to 300,000 cSt), alkyl-modified silicone oil, silicone polyether copolymer, and the like. It is commercially available as a solution, emulsion, or oil compound and can be easily obtained. One or two of these
One or more species can be used in combination.

The dyeing solution used in the plate making method of the waterless planographic printing plate of the present invention is a compound represented by the formula (1),
Contains water, surfactants and dyes. Preferred as such a compound represented by the formula (1) is R ¹ ,
R ³ and R ⁴ are an alkyl group having 1 to 20 carbon atoms or a phenyl group, and R ² is a hydrogen atom or 1 to 10 carbon atoms.
Alkyl group, the alkyl group for R ⁵ is a hydrogen atom, a hydroxyl group or a number of carbon atoms is 1 to 10, m is 1-8, a compound wherein n is 1-5. When m is 2 or more, R ² may be the same or different, R ⁴ may be the same or different, and when n is 2 or more, R ⁵ may be the same or different. The following are mentioned as a specific example of such a compound.

[0012]

[Chemical 1] The concentration of these compounds in the dyeing solution ranges from 0.1% by weight to 90%.
Weight% is preferable, and more preferably, it is selected within the range of 2% to 40% by weight.

As the surfactant used in the dyeing solution of the present invention, all of those exemplified as the surfactants which can be added to the developing solution can be mentioned, but preferably selected from anionic surfactants, particularly preferably Examples thereof include alkylnaphthalene sulfonates (Perex NBL and the like) having high solubilizing power, polyoxyethylene naphthyl ether sulfate ester salts (Newcol B-4SN and the like) and the like. The concentration of the surfactant in the dyeing solution is 0.01% by weight to
50% by weight is preferable, more preferably 0.1% by weight to
A range of 30% by weight is selected.

Examples of dyes used in the dyeing solution of the present invention include water-soluble disperse dyes, acid dyes and basic dyes. Particularly preferred are triarylmethane-based acid dyes and triarylmethane-based basic dyes. It is a dye. Specific examples of these include acid dyes such as ACID VIOLET 5B.
(Hodogaya Chemical), KITON BLUE A (CIBA), PATENT
BLUE AF (manufactured by BASF), RAKUTO BRILLIANT BLUE FCF (manufactured by Rakuto Chemical Co., Ltd.), BRILLIANT ACID BLUE R (manufactured by GEIGY),
KAYANOL CYANINE 6B (Nippon Kayaku), SUPRANOL CYANINE
G (FARBENFABRIKEN BAYER), ORIENT SOLUBLE BLUE O
BB (manufactured by Orient Chemical Industry), ACID BRILLIANT BLUE 5
G (Chugai Kasei), ACID BRILLIANT BLUE FFR (Chugai Kasei), ACID GREEN GBH (Takaoka Chemical Industry), ACID BRI
LLIANT MILLING GREEN B (manufactured by Hodogaya Chemical Co., Ltd.), as basic dyes, crystal violet, ethyl violet, Victoria pure blue, Victoria blue,
Methyl violet, DIABASIC MAGENTA (manufactured by Mitsubishi Chemical), AIZEN BASIC CYANINE 6GH (manufactured by Hodogaya Chemical),
PRIMOCYANINE BX CONC. (Sumitomo Chemical Co., Ltd.), ASTRAZON BLU
EG (FARBENFABRIKEN BAYER), DIACRYL SUPRA BRIL
LIANT 2B (manufactured by Mitsubishi Chemical), AIZEN CATHILON TURQUOISE B
LUE LH (Hodogaya Chemical), AIZEN DIAMOND GREEN GH (
Hodogaya Chemical Co., Ltd.), AIZEN MALACHITE GREEN (Hodogaya Chemical Co., Ltd.), and the like. Among these, particularly preferably used are crystal violet,
Examples include ethyl violet and Victoria Pure Blue. The concentration of the dye in the dyeing solution is preferably 0.01% by weight to 10% by weight, more preferably 0.05% by weight to 5% by weight.

If necessary, an organic solvent, a defoaming agent, a chelating agent, an acid, a base, a preservative and the like can be added to the dyeing solution of the present invention. As the organic solvent added to the dyeing solution, for example, diisobutyl ketone, methyl ethyl ketone, methyl isobutyl ketone, acetone, acetophenone, isophorone, diethyl succinate, methyl benzoate,
Diethyl oxalate, dimethyl phthalate, isobutyl acetate, benzyl benzoate, ethyl acetate, propyl acetate, butyl acetate, amyl acetate, hexyl acetate, methyl butyrate, ethyl butyrate, propyl butyrate, ethyl cellosolve acetate, ethylene glycol, ethylene glycol mono. −
Phenyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol diacetate, ethylene glycol benzyl ether, ethylene glycol mono-n-pentyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol- Mono-n-heptyl ether, ethylene glycol-mono-n-octyl ether, diethylene glycol, diethylene glycol di-n-butyl ether, diethylene glycol diacetate, diethylene glycol mono-acetate, diethylene glycol-
Mono-n-pentyl ether, diethylene glycol-
Mono-n-hexyl ether, diethylene glycol-
Mono-n-heptyl ether, diethylene glycol-
Mono-octyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether,
Propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol,
Polypropylene glycol, triethylene glycol,
Tetraethylene glycol, polyethylene glycol,

Triethylene glycol dimethyl ether, triethylene glycol monomethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol dimethyl ether, ethyl ether, dioxane, tetrahydrofuran, n-amyl alcohol, benzyl alcohol , Cyclohexanone, cyclohexanol, N-
Benzylethanolamine, anisyl alcohol, dimethylbenzylcarbitol, 2-N-ethylanilinoethanol, propylene glycol monophenyl ether, N-phenylethanolamine, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec- Butanol, t-butanol, 3-methoxybutanol, furfuryl alcohol, tetrahydrofurfuryl alcohol, 1,2-propion oxide, ethyl cellosolve, butyl cellosolve, formic acid, acetic acid, propanoic acid, butyric acid, acrylic acid, propiolic acid,
Caproic acid, cyclopropanecarboxylic acid, benzoic acid, 2
-Aminopropanoic acid, succinic acid, phthalic acid, maleic acid, fumaric acid, tartaric acid, oxalic acid, acetoacetic acid, malonic acid, citric acid and the like are used. Among these, one kind or two or more kinds can be used in combination, but a dye concentration is controlled by combining a poorly water-soluble organic solvent with an easily-soluble organic solvent, or a volatile organic solvent is used as a non-volatile solvent. In combination with an organic solvent to control the fluctuation of the liquid composition, or to combine an organic solvent soluble in the photosensitive layer with an organic solvent insoluble in the photosensitive layer to perform additional development (to ensure that the development is sufficient after development). In the dyeing process, it is possible to control the ability as the development intended to impart the function as an additional development) and the dyeing density, or to select a plurality of solvents at the same time depending on the purpose.

It can be added to the dyeing solution of the present invention,
As the defoaming agent, chelating agent, acid, base and preservative, those exemplified as those which can be added to the developing solution can be used. In the dyeing process, the waterless lithographic printing plate is immersed in a dyeing solution, but the plate surface may be rubbed with a brush or the like for the purpose of preventing uneven dyeing. It is possible to further develop the existing portion. In the plate making method of the waterless lithographic printing plate of the present invention, it is desirable to wash the plate surface with tap water after dyeing or developing, and further, after washing with water, it is preferable to dry with warm air of 40 ° C. or higher and 100 ° C. or lower. When the plate making method of the waterless lithographic printing plate of the present invention is carried out by an automatic processor, it is desirable that all the processing liquids are kept at a constant temperature by a temperature control mechanism. The temperature of all treatment liquids is usually controlled within a range of 15 ° C. to 60 ° C. by a heater linked with a temperature sensor. When the developer is tap water, the developer is discharged from the developer by the overflow mechanism while directly connecting the automatic developing machine to the tap water and supplying tap water to prevent the developer from spoiling and to prevent the development residue of silicone rubber from developing. Can be discharged. Similarly, tap water can be supplied to the washing liquid to prevent spoilage.

As described above, as a method of directly connecting the water supply and the automatic developing machine to supply the tap water into the automatic developing machine, a method of supplying the tap water when the automatic developing machine is used by opening and closing the tap of the water supply, a plate sensor, There is a method of supplying tap water at the time of plate printing or at regular time intervals by using an electromagnetic valve that operates in conjunction with a microcomputer. In addition, all processing liquids are fed by a liquid delivery system that works in conjunction with a liquid level sensor and microcomputer.
It is desirable to automatically replenish the processing solution. In this case, the composition of the replenisher may be the same as or different from that of the treatment liquid. For example, the concentration (C
The relationship between ₁ ) and the concentration of the same component (C ₂ ) in the replenisher is completely arbitrary, but 10 ≧ C ₂ / C ₁ ≧ 0 is often used. Further, the replenisher may contain a component which is not initially contained in the dyeing solution. Such ingredients include:
Examples thereof include antifoaming agents, chelating agents, preservatives, dyes, solvents and surfactants. Further, one processing solution may be supplemented with two or more kinds of replenishing solutions. In such cases, water, organic solvent,
A surfactant, an antifoaming agent, a dye or the like may be used alone or a solution prepared to have a high concentration may be used. Of course, the surfactant and dye may be used as they are in powder form.

The waterless planographic printing plate used in the plate making method of the present invention will be described below. The support of the waterless lithographic printing plate used in the present invention may be any one as long as it is used in a normal waterless lithographic printing plate. Examples thereof include metal plates such as aluminum, copper, zinc and steel, plastic films such as polyester, and coated paper. Among these, the aluminum plate is most preferably used. <Aluminum Support> The aluminum plate used as a support in the present invention is a plate-like body such as pure aluminum or an aluminum alloy containing aluminum as a main component and a slight amount of a foreign atom. The different atoms include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel and titanium. The content of these foreign atoms is 10% by weight or less. Aluminum which is suitable for the present invention is pure aluminum, but completely pure aluminum is difficult to produce due to refining technology, and therefore it is preferable that the content of foreign atoms is as low as possible. Further, it can be said that the aluminum alloy having the above content rate is a material that can be used in the present invention. As described above, the aluminum plate applied to the present invention is not specified in its composition, and conventionally known and officially used materials can be appropriately used. The aluminum plate used in the present invention has a thickness of about 0.1 to 0.5 mm.

<Degreasing Treatment> It is preferable that the aluminum plate is subjected to a degreasing treatment in advance. As a method for removing the rolling oil on the surface of such an aluminum plate, preferably, it is first treated with an acid aqueous solution. Any acid may be used as long as it is known as an acid for cleaning metals, and inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, phosphoric acid, sulfamic acid, chromic acid, etc. Examples thereof include acid, gluconic acid, oxalic acid, tartaric acid, formic acid, hydroxyacetic acid, EDTA (ethylenediaminetetraacetic acid) and its derivatives, and ammonium thioglycolate. Further, these acids may be mixed and used. The treatment method includes showering, dipping, and
Coatings such as bars and giesers are used. Such degreasing with acid is performed on at least the surface on the side where the photosensitive layer is provided, but it is more preferable that the back side is also degreased with acid. After degreasing treatment, a coating film such as a photosensitive layer may be directly provided, but further graining, anodic oxidation,
Surface treatment such as treatment with an aqueous solution of silicate such as sodium silicate or potassium silicate (also referred to as “silicate treatment”) may be performed. Of these, silicate treatment is preferable. However, such surface treatment is preferably performed after the degreasing step. Further, this support may be surface-treated with a silane coupling agent for the purpose of improving the adhesion to the coating film.

<Primer Layer> It is preferable to further coat a primer layer or the like on the above substrate for the purpose of preventing halation and for other purposes. As the primer layer, various types can be used for improving the adhesiveness between the substrate and the photosensitive resin layer, preventing halation, dyeing an image and improving printing characteristics. For example, JP-A-60-22
Various photosensitive polymers disclosed in Japanese Patent No. 9031, which are exposed and cured before laminating a photosensitive resin layer, and epoxy resins disclosed in Japanese Patent Laid-Open No. 62-50760 are heated. What is cured, JP-A-63-
The gelatin disclosed in Japanese Patent No. 133151, which is hardened, is further disclosed in Japanese Patent Application Laid-Open No. 3-273248, which uses the urethane resin and the silane coupling agent disclosed in Japanese Patent Application Laid-Open No. 3-200965. Using urethane resin and diazo resin, European patent publication E
Examples thereof include those obtained by irradiating a coating film comprising a hydroxyl group-containing polymer and a diazo resin described in PO394924A specification with UV light to cure the coating film. In addition, those obtained by hardening gelatin or casein are also effective.
Among these, a primer layer containing a urethane resin and a diazo resin or a primer layer obtained by irradiating and curing this with UV light is particularly preferable. 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, and the primer layer may be formed only with the additive as long as it is within the range in which 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), and additives such as pigments and silica powder can also be included. Generally, the coating amount of the primer layer is appropriately in the range of 0.1 to 20 g / m ^{2 on} a dry weight basis, preferably 1 to 10 g / m ² .

<Photosensitive Layer> Examples of the photosensitive layer used in the present invention include a photopolymerizable photosensitive layer, a photocrosslinking type photosensitive layer and a photosensitive layer composed of a diazo resin and a binder resin, and preferably a photopolymerizable photosensitive layer. is there. The photopolymerizable photosensitive layer comprises at least (1) a monomer, an oligomer or a macromonomer having at least one photopolymerizable ethylenically unsaturated group, (2) a polymer compound having film forming ability, and (3) light. Contains a polymerization initiator.

Component (1): at least one photopolymerizable
Monomers and oligomers that have a functional ethylenically unsaturated group
Macromonomers Examples of the above-mentioned monomers, oligomers or macromers that can be used in the present invention include (A) alcohols (for example, ethanol, propanol, hexanol, 2-ethylhexanol, cyclohexanol, glycerin, hexanediol, trimethylolpropane). , Pentaerythritol, sorbitol, triethylene glycol, polyethylene glycol, polypropylene glycol, etc.) acrylic acid or methacrylic acid ester (B) amines (eg, ethylamine, butylamine, benzylamine, ethylenediamine, hexamethylenediamine, diethylenetriamine, xylylenediamine) , Ethanolamine, aniline, etc.) and glycidyl acrylate, glycidyl methacrylate or allyl glycy (C) Carboxylic acids (eg, acetic acid, propionic acid, benzoic acid, acrylic acid, methacrylic acid, succinic acid, maleic acid, phthalic acid, tartaric acid, citric acid, etc.) and glycidyl acrylate, methacrylic acid Reaction product with glycidyl acid or allyl glycidyl, (D) amide derivative (eg, acrylamide, N-methylol acrylamide, t-butyl acrylamide,
Methylene bis acrylamide, diacetone acrylamide, etc.) and the like.

Further, urethane acrylates as 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, the Japan Adhesive Association magazine Vol.
20, No. 7, pages 300 to 308 (1984), etc., described as photocurable monomers and oligomers, P. Dreyfuss & RPQuirk, Encycl.Polym.Sc.
i.Eng., 7, 551 (1987), Chemical Industry, 38, 56 (19
87), polymer processing, 35, 262 (1986), and other macromonomers 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. Also,
These may be used alone or in combination. The amount used is 5% by weight to 80% by weight, preferably 30% by weight to 7% by weight based on the total solid content of the photopolymerizable photosensitive layer.
It is 0% by weight.

Ingredient (2): a high film-forming ability
Molecular compound As the polymer compound having film-forming ability used in the present invention, polyester resin, vinyl chloride-vinyl acetate copolymer, acrylic resin, vinyl chloride resin, polyamide resin, epoxy resin, (meth) acrylate copolymer Polymers, (meth) acrylamide-based copolymers, polyurethane resins, vinyl acetate-based copolymers, polystyrene, phenoxy resins, polyvinyl chloride, acidic cellulose derivatives, alcohol-soluble polyamides, (meth) acrylic acid copolymers, maleic acid Examples thereof include a copolymer, polyvinyl alcohol, water-soluble polyamide, water-soluble urethane, water-soluble cellulose, polyvinylpyrrolidone and the like.
Further, as the polymer compound capable of forming a film, a polymer compound having a photopolymerizable or photocrosslinkable olefinic unsaturated double bond group in its side chain can be used, but is not limited thereto. Not a thing.

Component (3): Photopolymerization Initiator The following are typical examples of the photopolymerization initiator used in the present invention. a) a benzophenone derivative such as benzophenone,
Michler's ketone, xanthone, anthrone, thioxanthone, acridone, 2-chloroacridone, 2-chloro-N-n-butylacridone, 2,4-diethylthioxanthone, fluorenone, etc. b) Benzoin derivative, for example, benzoin, benzoinmethyl Ether, benzoin ethyl ether, etc. c) Quinones, for example, p-benzoquinone, β-naphthoquinone, β-methylanthraquinone, etc. d) Sulfur compounds, for example, dibenzyl disulfide, di-n-butyl disulfide, etc. e) Azo Alternatively, diazo compounds such as 2-azobisisobutyronitrile, 1-azo-bis-1-cyclohexanecarbonitrile, p-diazobenzylethylaniline, Congo red, etc. f) Halogen compounds such as carbon tetrabromide, odor Silver oxide, α
-Chloromethylnaphthalene, trihalomethyl-s-triazine compounds, etc. g) Peroxides such as benzoyl peroxide, etc. These may be used alone or in combination. The amount of these photopolymerization initiators added is 0.1 to 25% by weight, preferably 3 to 20% by weight, based on the total photosensitive layer composition.
Is.

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, a dye or pigment for the purpose of coloring the photosensitive layer, A pH indicator and a leuco dye may be added as a printing agent. Depending on the purpose, a small amount of polydimethylsiloxane, methylstyrene-modified polydimethylsiloxane, olefin-modified polydimethylsiloxane, polyether-modified polydimethylsiloxane, silane coupling agent, silicone diacrylate, silicone dimethacrylate, or other silicone compound in the photosensitive layer. May be added. 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. 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 composition of the photosensitive layer. A hydrophobic silica powder treated with a (meth) acryloyl group- or allylic group-containing silane coupling agent in some cases was added to the total photosensitive layer composition in an amount of 50.
It may be added in an amount of not more than wt%.

Further, the diazo resin used for the photosensitive layer comprising a diazo resin and a binder resin is a condensate of an aromatic diazonium salt and formaldehyde,
Of these, particularly preferred is a salt of a condensate of p-diazodiphenylamine with formaldehyde or acetaldehyde, for example, a reaction of hexafluorophosphate, tetrafluoroborate, perchlorate or periodate with the condensate. Examples include a diazo resin inorganic salt which is a product, and a diazo resin organic salt which is a reaction product of the condensate and a sulfonic acid as described in US Pat. No. 3,200,309. . The proportion of the diazo resin of the present invention in the photosensitive layer is 20 to 95% by weight, preferably 35 to 80% by weight. As the binder resin, various polymer compounds can be used, but preferably, a monomer having an aromatic hydroxyl group as described in JP-A-54-98613, such as N- (4-hydroxyphenyl). ) Copolymers of acrylamide, N- (4-hydroxyphenyl) methacrylamide, o-, m- or p-hydroxystyrene, o-, m- or p-hydroxyphenylmethacrylate with other monomers, USA A polymer containing a hydroxyethyl (meth) acrylate unit as a main repeating unit as described in Japanese Patent No. 4,123,276, JP-A-3-15
No. 8853, a copolymer resin having a monomer unit having a phenolic hydroxyl group and a monomer unit having an alcoholic hydroxyl group, a natural resin such as shellac or rosin, polyvinyl alcohol, U.S. Pat. No. 3,751,257. Polyamide resins as described in U.S. Pat. No. 3,660,097, linear polyurethane resins as described in U.S. Pat. No. 3,660,097, phthalated resins of polyvinyl alcohol, bisphenol A and epichlorohydrin. Epoxy resin condensed from, celluloses such as cellulose acetate and cellulose acetate are used.

In addition, those containing a photosensitive polymer as a main component such as polyesters, polyamides, and polycarbonates containing --CH.dbd.CH--CO-- as a photosensitive group in the main chain or side chain of the polymer are also included. . Examples thereof include a photosensitive polyester obtained from a condensate of phenylenediethyl acrylate and water-added bisphenol A and triethylene glycol as described in JP-A-55-40415, U.S. Pat. Second,
Photosensitive polyesters derived from (2-propenylidene) malonic acid compounds such as cinnamylidene malonic acid and difunctional glycols as described in US Pat. No. 956,878. Dyes, surfactants, plasticizers, stabilizers and the like can also be added to the photosensitive layer using the above diazo resin. The above-mentioned photosensitive layer composition used in the present invention is, for example, 2-methoxyethanol or 2-methoxyethanol.
On a substrate, dissolved in a suitable solvent such as methoxyethyl acetate, propylene glycol methyl ethyl acetate, methyl lactate, ethyl lactate, propylene glycol monomethyl ether, ethanol, methyl ethyl ketone, N, N-dimethylacetamide, etc. alone or in a mixed solvent thereof. Applied to. The coating weight is 0.1 after being dried.
The range of ^{20 to 20} g / m ² is suitable, and preferably 0.5.
The range is from 10 g / m ² .

<Ink Repellent Layer> As the ink repellent layer used in the present invention, a crosslinked silicone rubber layer, a fluororesin layer or the like can be used. The crosslinked silicone rubber layer used in the present invention is a partially or wholly crosslinked polydiorganosiloxane and has the following repeating units. —Si (R) ₂ —O— Here, R represents an alkyl, aryl, alkenyl or a monovalent group in which these are combined, and these groups are a halogen atom, amino, hydroxy, alkoxy, aryloxy, (meth). It may have a functional group such as acryloxy or thiol. In the silicone rubber layer, if necessary, fine powders of inorganic materials such as silica, calcium carbonate, titanium oxide, silane coupling agents, adhesion assistants such as titanate coupling agents and aluminum coupling agents, and photopolymerization. You may add an initiator.

Si based on the above polysiloxane as the main skeleton
With a molecular weight of several thousand to several hundred thousand as a raw material for silicone rubber
Polysiloxanes with functional groups are used, which are
Silicone rubber layer is formed by crosslinking and curing by the method shown
To be done. That is, specifically, water is added to both ends or one end
The above polysiloxane having an acid group has the following general formula
The silane-based cross-linking agent shown in
Metal compounds (eg organotin compounds, inorganic acids, amines
Etc.) catalyst to add polysiloxane and silane-based cross-linking
Formed by heating the agent and condensation curing at room temperature
To be done. R_nSiX_4-n Here, n is an integer of 1 to 3 and R is the same as R shown above.
Is a substituent, X is -OH, -OR², -OAc, -O
-N = CR²R³, -Cl, -Br, -I and other substituents
Represents Where R², R³Is the same as R described above
Definition, R ², R³May be the same or different
good. In addition, Ac represents an acetyl group. Also, water at the end
An organopolysiloxane having an acid group and a hydrogen
Polysiloxane cross-linking agent and optionally the above silane-based
Silicone rubber by condensation curing with a crosslinking agent
You may form a layer.

An addition type silicone rubber layer which is crosslinked by an addition reaction of ≡SiH group and —CH═CH— group is also useful. The addition type silicone rubber layer has an advantage that it is relatively insensitive to humidity at the time of curing, can be crosslinked at a high speed, and can easily obtain certain physical properties. The addition-type silicone rubber layer used here is obtained by reacting a polyvalent hydrogenorganopolysiloxane with a polysiloxane compound having two or more —CH═CH— bonds in one molecule, and is preferably ,
It is a composition obtained by crosslinking and curing a composition comprising the following components (1) to (3). (1) 100 parts by weight of organopolysiloxane having at least two alkenyl groups (preferably vinyl groups) directly bonded to silicon atoms in one molecule (2) Organohydrogen poly having at least two SiH bonds in one molecule Siloxane 0.1 to 1000 parts by weight (3) Addition catalyst 0.00001 to 10 parts by weight The alkenyl group of component (1) may be at the end of the molecular chain or in the middle, and as the organic group other than the alkenyl group,
It is a substituted or unsubstituted alkyl group or aryl group.
The component (1) may contain a small amount of hydroxyl groups. The component (2) reacts with the component (1) to form a silicone rubber layer, but plays a role of imparting adhesiveness to the photopolymerizable photosensitive layer. The hydrogen group of the component (2) may be at the terminal or in the middle of the molecular chain, and the organic group other than hydrogen is selected from the same as the component (1). The organic groups of the components (1) and (2) preferably have a methyl group content of 60% or more of the total number of the groups from the viewpoint of improving the ink repellency. The molecular structure of the component (1) and the component (2) may be linear, cyclic or branched, and it is preferable that at least one of them has a molecular weight of more than 1,000 from the viewpoint of rubber physical properties. It is preferable that the molecular weight of 1) exceeds 1,000.

Examples of the component (1) include α, ω-divinylpolydimethylsiloxane, a (methylvinylsiloxane) (dimethylsiloxane) copolymer having methyl groups at both ends, and the like as the component (2). Examples thereof include hydrogen-containing polydimethyl siloxane, α, ω-dimethyl polymethyl hydrogen siloxane, (methyl hydrogen siloxane) (dimethyl siloxane) copolymer having both terminal methyl groups, and cyclic polymethyl hydrogen siloxane. The addition catalyst of the component (3) is arbitrarily selected from known ones, but a platinum-based compound is particularly desirable, and platinum simple substance, platinum chloride, chloroplatinic acid, olefin coordinated platinum and the like are exemplified. For the purpose of controlling the curing rate of these compositions, vinyl group-containing organopolysiloxanes such as tetracyclo (methylvinyl) siloxane, carbon-carbon triple bond-containing alcohols, acetone, methylethylketone, methanol and ethanol. It is also possible to add a crosslinking inhibitor such as propylene glycol or propylene glycol monomethyl ether. These compositions are characterized in that an addition reaction occurs at the time when the three components are mixed and curing begins, but the curing rate rapidly increases as the reaction temperature increases. Therefore, for the purpose of prolonging the pot life until rubberization of the composition and shortening the curing time on the layer, the curing condition of the composition is a temperature within a range in which the characteristics of the substrate and the photopolymerizable photosensitive layer do not change. It is preferable to keep the temperature under the conditions and until it is completely cured, from the viewpoint of the stability of the adhesive force with the photopolymerizable photosensitive layer. In addition, the components (1) and (3) above and the coating solvent are used in consideration of the pot life of the coating liquid during production.
It is preferable that the component (2) and the coating solvent are separately prepared and mixed immediately before coating. At this time, the crosslinking inhibitor is the component (2)
It is preferable to prepare the solution together with it. In addition to these compositions, alkenyltrialkoxysilane,

[0034]

[Chemical 2]

[0035]

[Chemical 3]

Addition of a known adhesiveness-imparting agent such as, for example, a hydroxyl group-containing organopolysiloxane which is a component of the condensation type silicone rubber layer, a dimethylpolysiloxane having a trimethylsilyl group at the terminal, a phenylmethylpolysiloxane copolymer Silicone oil and hydrolyzable functional group-containing silane (or siloxane) may be added. Further, a known filler such as silica may be added to improve the rubber strength. As the crosslinked fluororesin layer, for example, those described in JP-A-58-215411 and JP-A-2-103047 can be used. Specifically, it has the following structural units in the molecule, CF _3- , -CF _2- , = CF-, CF ₃ -O-, -CF ₂ -O-, = CF-O- ( Fluorine content is 30% by weight or more, preferably 50% by weight or more) and a functional group capable of reacting with a crosslinking agent in its molecule,
Alternatively, epoxy _{groups, -OH, -COOH, -NH 2,} -NCO, -NH-
And the like, which are polymer compounds having functional groups capable of cross-linking each other, and which are obtained by copolymerizing a fluorine-containing (meth) acrylic monomer, a fluorine-containing olefin monomer, a (meth) acrylic monomer, or a vinyl monomer. However, the present invention is not limited to this.

The ink repellent layer in the present invention has a small thickness.
If this happens, the ink repellency will decrease and scratches will easily occur.
If there is a point and the thickness is large, the developability will be poor.
From the point, the thickness is 0.5 to 5 g / m.²Is preferred,
More preferably 1-3 g / m ²Is. Explained here
In the waterless planographic printing plate, further seeds are formed on the ink repellent layer.
Various ink repellent layers may be applied. Also, remove the photosensitive layer
The purpose is to increase the adhesion between the repulsion layer and
To prevent the poisoning of the catalyst in the repulsion layer composition,
An adhesive layer may be provided between the layer and the ink repellent layer. Change
On the ink repellent layer to protect the surface of the ink repellent layer.
Transparent film such as polyethylene, polypropylene
Polyvinyl chloride, polyvinylidene chloride, polyvinyl
Alcohol, polyethylene terephthalate, cellophane
Etc. laminated or coated with polymer
May be. These films may be stretched before use.
In addition, this film has a true
To improve the air adhesion, matte or silica
No matter which powder is used for coating the polymer
good.

These waterless lithographic printing plates are exposed imagewise by a UV lamp and imagewise exposed by a UV lamp or imagewise by scanning laser light. After that, it is developed and dyed by the plate-making method of the present invention, but it can be sensitized by performing a heat treatment as a pretreatment.
In addition, workability can be significantly improved by automatically performing the process from exposure to development using an automatic transport mechanism, and in the plate making method in which exposure is performed by scanning laser light,
Particularly preferably used.

[0039]

According to the plate making method of the present invention, the plate surface after plate making has excellent scratch resistance and developability. The reason why the plate surface of the waterless planographic printing plate can be prevented from being damaged is that when the plate surface of the developing solution is immersed in the dyeing solution, the compound represented by the formula (1) is contained in the organic layer below the non-image area silicone rubber layer. It is considered that the permeation and softening reduce the external force applied to the surface of the silicone rubber layer, and the silicone rubber layer is less likely to be scratched. Further, according to this plate-making method, the compound represented by the formula (1) does not penetrate into the photosensitive layer at the time of development, so that there is a remarkable advantage that good developability is maintained.

The present invention will be described in more detail with reference to the following examples. Example 1 (primer layer) A 0.3 mm thick JI degreased by a conventional method.
KBA613 (manufactured by Shin-Etsu Chemical Co., Ltd.), which is an aminosilane coupling agent, made of S A 1050 aluminum plate 1
% Aqueous solution and then dried at room temperature. A primer coating solution having the following composition was applied on the aluminum plate so that the dry weight was 4 g / m ^2, and the coating was heated at 140 ° C. for 2 minutes to be dried. Primer coating liquid・ Samprene IB1700D (manufactured by Sanyo Kasei Co., Ltd.) 10 parts by weight ・ 0.1 part by weight of hexafluorophosphate of polycondensation product of p-diazodiphenylamine and paraformaldehyde ・ 0.1 part by weight of TiO ₂ Defencer MCF323 (manufactured by Dainippon Ink and Chemicals, Inc.) 0.03 parts by weight-Propylene glycol methyl ether acetate 50 parts by weight-Methyl lactate 20 parts by weight-Pure water 1 part by weight Then, Nuark FT261V UDNS ULTRA-PLUS
The FLIPTOP PLATE MAKER vacuum exposure machine was used for 20 count exposures.

(Photosensitive Layer) A photopolymerizable photosensitive layer coating solution having the following composition was applied onto an aluminum plate coated with the above primer.
It was applied so that the dry weight was 5 g / m ^2, and dried at 100 ° C. for 1 minute. Photopolymerizable photosensitive layer coating liquid composition -Polyurethane resin (isophorone diisocyanate / polyester (adipic acid / 1,4-butanediol / ethylene glycol) / 1,4-butanediol / isophoronediamine) 1.5 parts by weight A-600 (Polyethylene glycol diacrylate manufactured by Shin-Nakamura Chemical Co., Ltd.) 0.4 parts by weight-Addition product of xylylenediamine 1 mol / glycidyl dimethacrylate 4 mol 1.0 parts by weight-Ethyl Michler's ketone 0.35 parts by weight-2 , 4-dichlorothioxanthone 0.10 part by weight-Victoria Pure Blue BOH naphthalene sulfonate 0.01 part by weight-Defencer MCF323 (Dainippon Ink and Chemicals, Inc.) 0.03 part by weight-Methyl ethyl ketone 10 parts by weight・ Propylene glycol methyl ether 25 parts by weight

(Ink Repellent Layer) The following silicone rubber layer coating liquid was dried on the above photopolymerizable dry layer to a dry weight of 2 g / m ^2.
And was dried at 140 ° C. for 2 minutes. Silicone rubber layer coating liquid composition・ CH ₂ = CH-(-Si (CH ₃ ) ₂ -O-) ₅₀₀ -Si (CH ₃ ) ₂ -CH = CH ₂ 9 parts by weight ・ (CH ₃ ) ₃ Si-O- _{(-SiH (CH 3) -0-)} 8 -Si (CH 3) 3 0.4 part by weight of polydimethylsiloxane (degree of polymerization 8,000) 0.3 parts by weight olefin - chloroplatinic acid 0.2 part _{· HC≡CC (CH 3) 2 -O} -Si of (CH _{3) 3} 0.1 parts by weight Isopar G (manufactured by Esso chemical Co.) 140 parts by weight obtained as described above silicone rubber layer A 12 μm-thick, single-sided matted biaxially oriented polypropylene film was laminated on the surface so that the non-matted surface was in contact with the silicone rubber layer to obtain a waterless photosensitive lithographic printing plate.

A 200 line / inch halftone dot chart is overlaid on this printing plate, and FT261V UDNS ULTRA-P manufactured by Nuark
LUS FLIPTOP PLATE MAKER After exposing for 30 counts using a vacuum exposure machine, peel off the laminate film, rub the plate surface with a pad soaked in tap water, remove the silicone rubber layer on the image area, and then The dyeing solution was soaked in the pad, and the plate surface was lightly wiped for 30 seconds to dye the image area where the silicone rubber layer was removed. The staining density of the image area was 1.30 when measured with a Macbeth reflection densitometer. Dyeing liquid composition-Ethyl violet 0.2g-Exemplified compound (a) 10g-Newcol B4SN (Anionic surfactant made by Nippon Emulsifier) 10g-Water 80g Heidelberg GTO printing with the dampening water supply device removed using this plate Machine Toyo Ink TOYO KI
NG ULTRA TUK AQUALESG G When printed with black ink, there were no scratches and stains caused by scratches when handling the plate, and even after printing 120,000 sheets, it was a beautiful print that faithfully reproduced the original image without scratches and stains due to paper dust. was gotten.

Comparative Example 1 In Example 1, plate making was carried out using the following dyeing solution. Staining liquid composition-Ethyl violet 0.2 g-Carbitol 14 g-Water 86 g When the plate thus obtained was evaluated for scratches and stains in the same manner as in Example 1, scratches and stains due to handling of the plate were found everywhere. When 120,000 sheets were printed, scratches and stains, which are considered to be caused by paper dust, occurred.

Example 2 In Example 1, a dyeing solution having the following composition was used to make a plate. The staining density of the image area was 1.35 when measured with a Macbeth reflection densitometer. Dyeing liquid composition-Ethyl violet 0.2g-Exemplified compound (h) 5g-Perex NBL (Anionic surfactant made by Kao Soap) 15g-Water 80g Heidelberg GTO printer using this plate and removing the dampening water supply device At Toyo Ink TOYO KI
When printed with NG ULTRA TUK AQUARES G black ink, there was no scratch and stain caused by scratches when handling the plate, and even when 120,000 sheets were printed, a beautiful print faithfully reproducing the original image without scratches and stains due to paper dust was obtained. Was obtained.

Example 3 In Example 1, a dyeing solution having the following composition was used to make a plate. The staining density of the image area was 1.40 when measured with a Macbeth reflection densitometer. Dyeing liquid composition-Ethyl violet 0.2g-Exemplified compound (g) 5g-Perex NBL (Anionic surfactant manufactured by Kao Soap) 15g-Water 80g Heidelberg GTO printing machine with the dampening water supply device removed using this plate At Toyo Ink TOYO KI
When printed with NG ULTRA TUK AQUARES G black ink, there was no scratch and stain caused by scratches when handling the plate, and even when 120,000 sheets were printed, a beautiful print faithfully reproducing the original image without scratches and stains due to paper dust was obtained. Was obtained.

Claims (2)

[Claims] 1. A dyeing solution for a waterless lithographic printing plate, which comprises a photosensitive layer and a silicone rubber layer laminated in this order on a substrate, which contains a compound represented by formula (1), water, a surfactant and a dye. A waterless lithographic printing plate dyeing solution characterized by the following: R ¹ -CO-O-CH ₂ -[-C (R ² ) (-O-CO-R ⁴ )-] _m -[-CH (R ⁵ )-] _n -O-CO-R ³ (1) (Wherein R ¹ , R ³ and R ⁴ are the same or different and each represent a substituted or unsubstituted alkyl group, a phenyl group or an aralkyl group, and R ² represents a hydrogen atom, a substituted or unsubstituted alkyl group, R ⁵ is a hydrogen atom, a hydroxyl group, or
A substituted or unsubstituted alkyl group is shown. Also, m and n
Is an integer of 1 or more. ) 2. A waterless photosensitive lithographic printing plate obtained by sequentially laminating a photosensitive layer and a silicone rubber layer on a substrate, after imagewise exposure,
A photosensitive layer and / or a primer layer exposed by removing a silicone rubber by developing with a developing solution consisting essentially of water are selectively dyed with the dyeing solution according to claim 1. Waterless planographic printing plate making method.