JP2729880B2 - No fountain solution photosensitive lithographic printing plate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive film which does not require a dampening solution, which has a silicone rubber layer peeling (film edge) due to pressure desensitization at an original film edge portion, and has greatly improved ground stain resistance and printing durability during printing. Related to lithographic printing plates.

[0002]

2. Description of the Related Art Various types of photosensitive lithographic printing plates requiring no fountain solution for performing lithographic printing without using fountain solution (hereinafter referred to as waterless lithographic printing plates) have been proposed. Among them, Japanese Patent Publication No. 54-26923 and Japanese Patent Publication No. 55-227
No. 81, JP-B-56-23150 and JP-A-2-2-2.
No. 36550, in which a primer layer, a photosensitive layer and a silicone rubber layer are coated in this order on a support, has extremely excellent performance. The silicone rubber layer used in these waterless lithographic printing plates usually contains a high-molecular polymer mainly composed of polysiloxane,
What has been partially cross-linked using a cross-linking agent is used. As a method for curing the silicone rubber layer, the following two methods are usually used. (1) Condensation type: a method in which a polysiloxane having hydroxyl groups at both ends is crosslinked with a silane or siloxane having a hydrolyzable functional group directly bonded to a silicon atom to form a silicone rubber. (2) Addition type: polysiloxane having -SiH group and -C
A method in which a polysiloxane having an H = CH- group is subjected to an addition reaction to obtain a silicone rubber (Japanese Patent Laid-Open No. 61-7 / 1986)
No. 3156, Japanese Patent Application Laid-Open No. 3-161753, etc.). The condensation type silicone rubber of (1) changes its curability and adhesive strength with the photosensitive layer depending on the amount of moisture in the atmosphere during curing, so that when a lithographic printing plate without water is used, the sensitivity is likely to fluctuate and stable production is possible. It has the disadvantage of being difficult. In that respect,
It is considered that the addition type silicone rubber (2), which does not have such a defect, is superior.

However, when the addition type silicone rubber is used, the background stain resistance during printing (background stain: ink slightly adheres to the paper surface of the non-image area where ink should not originally adhere), and resistance to soiling. It was a problem to balance the printability.
In other words, if the degree of cure of the addition type silicone rubber is too high, the printing durability is improved but the background stain resistance is deteriorated. If the degree of curing is too low, the background stain resistance is improved, but the printing durability is reduced. As described above, the background stain resistance and the printing durability are completely opposite to each other, and it has been a problem to make them compatible. on the other hand,
In order to prevent “burning blur” at the time of document exposure, vacuuming is usually performed to improve the adhesion between the document film and the printing plate. Since the waterless lithographic printing plate uses soft silicone rubber, the edge of the original film is deformed by the pressure caused by vacuuming and desensitized. For this reason, there is a phenomenon that the silicone rubber layer is peeled off during development and becomes an image portion during printing. In order to prevent this, a method of performing "burn-out" by increasing the exposure amount or erasing by using an erasing liquid is usually performed, but it is inefficient as a plate making operation, and improvement has been strongly desired.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a waterless lithographic printing plate in which the silicone rubber layer is not peeled off due to pressure desensitization at the edge of the original film, and the ground stain resistance and printing durability are significantly improved. To provide a version.

[0005]

An object of the present invention is to provide a photosensitive lithographic printing plate in which a photosensitive layer and a silicone rubber layer are laminated in this order on a support. a) in one molecule, the polysiloxane having at least two alkenyl groups bonded directly to the silicon atom - (Si (R ¹⁾
(R ² ) -O) _l -group (wherein R ¹ and R ² represent an alkyl group, an aryl group, an aralkyl group, a vinyl group or a halogenated hydrocarbon group, provided that 70% or more of R ¹ and R ² Is a methyl group.) When (i) 100 ≦ l ≦ 5
50 to 95% by weight of the polysiloxane of (ii) 70
5 to 50% by weight of polysiloxane having 0 ≦ l ≦ 10000
(I) + (ii) = 100% by weight) and b) a hydrogen polysiloxane of the following general formula (I) R ³ —Si (R ⁴ ) ₂ —O— (SiH (R ⁴ ) — O) _m- (Si (R ⁴ ) ₂ -O) _n -Si (R ⁴ ) ₂ -R ³ (I) (wherein R ³ represents a hydrogen atom or a methyl group, R ⁴ represents an alkyl group, an aryl group, Represents an alkyl group, an aralkyl group or a vinyl group, which may be the same or different, provided that 70% or more of R ⁴ is a methyl group, and m + n = 4 to 10
0, and n / m = 0-1. ) Is achieved by a photosensitive lithographic printing plate requiring no dampening solution, characterized in that it is crosslinked by an addition reaction. As described above, the addition type silicone rubber is one in which the alkenyl group of the base polymer reacts with the Si-H group in the crosslinking agent to cure. In the present invention, the use of hydrogenpolysiloxane having a high Si—H group ratio in one molecule increases the silicone rubber curing efficiency, increases the film strength, and the three-dimensional structure of the cured silicone rubber is unknown. By blending a high molecular weight base polymer with a low molecular weight base polymer as a main component, the ink repellency is increased, and the above object has been achieved.

Hereinafter, the present invention will be described in detail. The waterless lithographic printing plate of the present invention must have enough flexibility to be set in a normal printing machine and at the same time withstand the load applied during printing. Accordingly, typical substrates include coated paper, metal plates such as aluminum, plastic films such as polyethylene terephthalate, rubber, and composites thereof. The surface of these substrates can be further coated with a primer layer or the like for the purpose of preventing halation and for other purposes. Further, as disclosed in JP-A-4-3166, the surface of the substrate can be subjected to a surface treatment with a silane coupling agent in order to improve the adhesion between the substrate and the photosensitive layer or the primer layer. As the primer layer, various layers can be used for improving the adhesion between the substrate and the photosensitive resin layer, preventing halation, dyeing an image, and improving printing characteristics. For example, JP
Various types of photosensitive polymers as disclosed in JP-A-2-2903 are exposed and cured before laminating a photosensitive resin layer, and epoxy resins disclosed in JP-A-62-50760 are used. Heat cured, JP 6
Japanese Patent Application Laid-Open No. 3-133151 discloses a hardened gelatin disclosed in Japanese Patent Application Laid-Open No. 3-133151, a device using a urethane resin and a silane coupling agent disclosed in Japanese Patent Application Laid-Open No. 3-200965, and Japanese Patent Application Laid-Open No. 3-273248. And the like using a urethane resin disclosed in US Pat. In addition, a casein which is hardened is also effective.
Further, for the purpose of softening the primer layer, a polyurethane, a polyamide, a styrene / butadiene rubber, a carboxy-modified styrene / butadiene rubber, an acrylonitrile / butadiene rubber, an acrylonitrile / butadiene rubber, a carboxy-modified acrylonitrile having a glass transition temperature of not more than room temperature are contained in the primer layer. / Polymer 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 by the additive as long as the film layer can be formed. In addition, these primer layers may be provided with a dye, a pH indicator, a printing-out agent, a photopolymerization initiator, and an adhesion assistant (for example, a polymerizable monomer, a diazo resin, a silane coupling agent, a titanate coupling) in accordance with the purpose described above. , An aluminum coupling agent), an additive such as a pigment or a silica powder. In general, the coating amount of the primer layer is suitably in the range of 0.1 to 20 g / m ² by dry weight, and preferably 1 to 10 g / m ² . Examples of the photosensitive layer used in the present invention include a photopolymerizable photosensitive layer, a photocrosslinkable photosensitive layer, and a photosensitive layer composed of a diazo resin and a binder resin. The photopolymerizable photosensitive layer is a monomer having at least (1) at least one photopolymerizable ethylenically unsaturated group;
An oligomer or a macromonomer, (2) a polymer compound having a film forming ability, and (3) a photopolymerization initiator.

Component (1): at least one photopolymerizable
Monomers, oligomers, etc.
The monomer other that can be used in the macromonomer present invention, the oligomer or macromonomer, for example, (A) alcohols (e.g., ethanol, propanol, hexanol, 2-ethylhexanol, cyclohexanol, glycerin, hexanediol, tri Acrylic or methacrylic acid esters of methylolpropane, pentaerythritol, sorbitol, triethylene glycol, polyethylene glycol, polypropylene glycol, etc. (B) amines (for example, ethylamine, butylamine, benzylamine, ethylenediamine, hexamethylenediamine, diethylenetriamine, xylyl) Diamine, ethanolamine, aniline, etc.) and glycidyl acrylate, glycidyl methacrylate or allylglycol. Reaction product with gill; (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 products with glycidyl acid or allyl glycidyl, (D) amide derivatives (eg, acrylamide, N-methylolacrylamide, t-butylacrylamide,
Methylenebisacrylamide, diacetoneacrylamide, etc.).

Also, urethane acrylates described in JP-B-48-41708, JP-B-50-6034, and JP-A-51-37193;
Polyfunctional acrylates such as polyester acrylates described in JP-A-8-64183, JP-B-49-43191 and JP-B-52-30490; epoxy acrylates obtained by reacting an epoxy resin with (meth) acrylic acid; Methacrylates and N-methylolacrylamide derivatives described in U.S. Pat. No. 4,540,649 can be mentioned. In addition, Japan Adhesives Association Journal Vol.20,
No. 7, pages 300 to 308 (1984), etc., described as photocurable monomers and oligomers, P. Dreyfuss & RP Quirk, Encycl. Polym. Sci.
Eng., 7, 551 (1987), Chemical Industry, 38, 56.
(1987), Polymer Processing, 35, 262 (1986)
And the like can also be used. However, the present invention is not limited to these, and in the polyfunctional monomer, the unsaturated group may be present as a mixture of an acryl group, a methacryl group, an allyl group, a vinyl group and the like. These may be used alone or in combination. The amount used is from 5% by weight to 80% by weight, preferably 3% by weight, based on the total solid weight of the photopolymerizable photosensitive layer.
0 to 70% by weight.

Ingredient (2): a high-grade compound having film-forming ability
As the polymer compound having a film forming ability for use in children compound present invention, a polyester resin, vinyl chloride - vinyl acetate copolymer, acrylic resins, vinyl chloride resins, polyamide resins, epoxy resins, (meth) acrylate copolymerization Coalescence, (meth) acrylamide copolymer, polyurethane resin, vinyl acetate copolymer, polystyrene, phenoxy resin, polyvinyl chloride, acidic cellulose derivative, alcohol-soluble polyamide, (meth) acrylic acid copolymer, maleic acid Copolymers, polyvinyl alcohol, water-soluble polyamide, water-soluble polyurethane, water-soluble cellulose, polyvinyl pyrrolidone and the like can be mentioned. Further, as the polymer compound having a film forming ability, a polymer compound having a photopolymerizable or photocrosslinkable olefinically unsaturated double bond group in a side chain can be used, but is not limited thereto. Not something.

Component (3): Photopolymerization initiator The following are typical examples of the photopolymerization initiator used in the present invention. a) benzophenone derivatives such as benzophenone,
Michler's ketone, xanthone, anthrone, thioxanthone, acridone, 2-chloroacridone, 2-chloro-N-n-butylacridone, 2,4-diethylthioxanthone, fluorenone, etc. b) benzoin derivatives such as benzoin, benzoin methyl ether, 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 or diazo Compounds, for example, 2-azobisisobutyronitrile, 1-azo-bis-1-cyclohexanecarbonitrile, p-diazobenzylethylaniline, Congo red, etc. f) Halogen compounds, for example, carbon tetrabromide, silver bromide , Α
-Chloromethylnaphthalene, trihalomethyl-s-triazine compounds, etc. g) Peroxides, for example, benzoyl peroxide. These may be used alone,
They may be used in combination. The addition amount of these photopolymerization initiators is 0.1 to 25% by weight, preferably 3 to 20% by weight, based on the whole photosensitive layer composition.

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

Further, as a diazo resin used for a photosensitive layer comprising a diazo resin and a binder resin, there is a condensate of an aromatic diazonium salt and formaldehyde,
Among them, particularly preferred are salts of condensates of p-diazodiphenylamine with formaldehyde or acetaldehyde, for example, the reaction of hexafluorophosphate, tetrafluoroborate, perchlorate or periodate with the condensate. Examples thereof include a diazo resin inorganic salt which is a product and an organic salt of a diazo resin 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.
-98613, a monomer having an aromatic hydroxyl group, such as N- (4-hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) methacrylamide, o-, m- or Copolymers of p-hydroxystyrene, o-, m- or p-hydroxyphenyl methacrylate with other monomers, hydroxyethyl (meth) acrylate as described in U.S. Pat. No. 4,123,276 A polymer containing a monomer unit having a phenolic hydroxyl group and a monomer unit having an alcoholic hydroxyl group as described in JP-A-3-158853, or a natural resin such as shellac or rosin. Resin, polyvinyl alcohol, described in U.S. Pat.No. 3,751,257 Polyamide resin, linear polyurethane resin as described in U.S. Pat.No. 3,660,097, phthalated resin of polyvinyl alcohol, epoxy resin condensed from bisphenol A and epichlorohydrin, cellulose butyrate and cellulose acetate, etc. Are used.

Further, there may be mentioned those mainly composed of a photosensitive polymer such as polyesters, polyamides and polycarbonates containing -CH = CH-CO- as a photosensitive group in the main chain or side chain of the polymer. . Examples of such a polyester include a photosensitive polyester obtained by condensation of phenylenediethyl acrylate with water-added bisphenol A and triethylene glycol as described in JP-A-55-40415, U.S. Pat. 2,
There are (2-propenylidene) malonic acid compounds such as cinnamylidenemalonic acid as described in U.S. Pat. No. 956,878 and photosensitive polyesters derived from difunctional glycols. Dyes, surfactants, plasticizers, stabilizers and the like can be added to the photosensitive layer using the above diazo resin. The photosensitive layer composition used in the present invention includes, for example, 2-methoxyethanol, 2-methoxyethyl acetate, propylene glycol methyl ethyl acetate, methyl lactate, ethyl lactate, propylene glycol monomethyl ether, ethanol, methyl ethyl ketone, N, N- A suitable solvent such as dimethylacetamide or the like is dissolved alone or in a mixed solvent thereof, and applied on a substrate. The coating weight is 0.1 to 20 g after drying.
/ M ² is suitable, preferably 0.5 to 10 g.
/ M ² .

The silicone rubber layer used in the present invention comprises the following components. (a) As a base polymer, one molecule has at least two alkenyl groups (for example, vinyl, butenyl, hexenyl, decenyl and the like, more preferably vinyl groups) directly bonded to a silicon atom. -(Si (R ¹ ) (R ² ) -O) _l -group of polysiloxane (wherein R ¹ and R ² are an alkyl group such as a methyl group or an ethyl group, an aryl group such as a phenyl group, β- An aralkyl group such as a phenylpropyl group,
Represents a halogenated hydrocarbon group such as a vinyl group, a chloromethyl group, and a 3,3,3-trifluoropropyl group. However,
70% or more of R ¹ and R ² are methyl groups. ) Is from 50 to 95% by weight of a polysiloxane having 100 ≦ l ≦ 500, and (ii) 700 ≦ l ≦ 1000.
0 to 5% by weight of polysiloxane ((i) + (ii) = 10)
0% by weight). Three or more polysiloxanes may be mixed. Preferred mixing ratios are (i) :( ii)
= 60: 40 to 95: 5, more preferably (i):
(ii) = 70: 30 to 90:10. (b) The crosslinking agent used in the present invention is a hydrogenpolysiloxane represented by the above general formula (I). Among these hydrogen polysiloxanes, a particularly preferred one is a hydrogen polysiloxane represented by the following general formula. _{(CH 3) 3 -Si-O-} (SiH (CH 3) -O) m - (Si (CH 3) 2 -O) n -Si (CH 3) of the ₃ wherein m, as the n, preferably The following ratios are listed. (M; n) = (5-50; 0), (5-50; 5),
(10-80; 10), (20-80; 20) More preferably, (m; n) = (5-40; 0). Also, 2
More than one hydrogen polysiloxane may be used. The mixing ratio of the alkenyl polysiloxane and the hydrogen polysiloxane is such that the Si-H group of the hydrogen polysiloxane is at least 2 equivalents, preferably 4 to 15 equivalents, based on the carbon-carbon unsaturated groups of the alkenyl polysiloxane. desirable.

The catalyst for the addition reaction of the silicone rubber composition is arbitrarily selected from known catalysts, and is particularly preferably a platinum compound, such as platinum alone, platinum chloride, chloroplatinic acid, and olefin-coordinated platinum. Is done. For the purpose of controlling the curing speed of these compositions, vinyl group-containing organopolysiloxanes such as tetracyclo (methylvinyl) siloxane, carbon-carbon triple bond-containing alcohols,
It is also possible to add a crosslinking inhibitor such as acetone, methyl ethyl ketone, methanol, ethanol and propylene glycol monomethyl ether. These compositions are characterized in that an addition reaction occurs at the time of mixing and curing starts, but the curing rate rapidly increases as the reaction temperature increases. Therefore, for the purpose of extending the pot life until rubberization of the composition and shortening the curing time on the layer, the curing conditions of the composition are set at a temperature within a range where the characteristics of the substrate and the photopolymerizable photosensitive layer do not change. It is preferable to keep the temperature at high temperature under the condition and until it is completely cured. In addition to these compositions, a known adhesion-imparting agent such as alkenyl trialkoxysilane may be added, or fine powder of an inorganic substance such as silica, calcium carbonate, or titanium oxide, a silane coupling agent, or a titanate coupling may be used. A bonding agent such as an agent or an aluminum-based coupling agent, a silicone oil or a photopolymerization initiator may be added.

Further, in order to improve the releasability of a cover film provided for protecting the ink repellent layer, Japanese Patent Application Laid-Open No. 1-19044 discloses a method.
No. 7, a silicone compound represented by the following general formula (II) may be added to the silicone rubber layer. (R ⁵ ) ₃ -SiO- (Si (R ⁵ ) ₂ -O) _p- (Si (R ⁶ ) (R ⁷ ) -O) _q -Si (R ⁵ ) ₃ (II) (where R ⁵ is R ⁶ and R ⁷ are a (substituted) alkyl group or a (substituted) aromatic group, and R ⁶ and R ⁷ are the same or different. One of them may be a (substituted) aromatic group, p: q = 99: 1 to 10:90 molar ratio) Specific examples include the following compounds, but are not limited thereto. Absent. (CH ₃ ) ₃ SiO- (Si (CH ₃ ) ₂ -O) _p- (Si (CH ₃ ) (CH ₂ CH (CH ₃ ) -C ₆ H ₅ )) _q -O-Si (CH ₃ ) ₃ p: q = 75: 25, M _w = about 2 × 10 ⁴ Alternatively, a generally known release agent may be added.

The ink repellent layer according to the present invention has a problem that if the thickness is small, the ink repellency is reduced, and the ink repellent layer is easily damaged, 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 herein, various ink repellent layers may be further coated on the ink repellent layer. Further, for the purpose of increasing the adhesive force between the photopolymerizable photosensitive layer and the ink repellent layer, or to prevent poisoning of the catalyst in the ink repellent layer composition, the photopolymerizable photosensitive layer and the ink repellent layer An adhesive layer may be provided between them. Furthermore, to protect the surface of the ink repellent layer,
A transparent film, for example, polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyethylene terephthalate, cellophane, or the like may be laminated on the ink repellent layer, or a polymer coating may be applied. These films may be used after being stretched. Further, the film may be provided with a mat in order to improve the vacuum adhesion in a printing frame during image exposure.

The waterless lithographic printing plate according to the present invention is developed with a developer capable of dissolving or swelling a part of the photosensitive layer in the image area (unexposed area) after exposure through the transparent original image. As the developer used in the present invention, those known as developers for waterless lithographic printing plates can be used, and water or an aqueous solution of a water-soluble organic solvent containing water as a main component is preferable. Considering safety and flammability, the concentration of the water-soluble solvent is 4
Less than 0% by weight is desirable, and development with water alone is particularly desirable. Known compounds include, for example, aliphatic hydrocarbons (hexane, heptane, “ISOPAR E, H, G” (manufactured by Esso Chemical Co., Ltd.) or gasoline, kerosene, etc.), and aromatic hydrocarbons (toluene, xylene, etc.). ) Or a halogenated hydrocarbon (trichlene or the like) to which the following polar solvent has been added, or the polar solvent itself. ・ Alcohols (methanol, ethanol, propanol, isopropanol, benzyl alcohol, ethylene glycol monomethyl ether, 2-ethoxyethanol, Diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, polyethylene glycol monomethyl ether -Ketones (acetone, methyl ethyl ketone, etc.)-Esters (ethyl acetate, methyl lactate, butyl lactate, etc.)
Propylene glycol monomethyl ether acetate,
Diethylene glycol acetate, diethyl phthalate, etc.)-Others (triethyl phosphate, tricresyl phosphate, etc.) Also, water can be added to the organic solvent-based developer or the organic solvent can be added to water using a surfactant or the like. Solubilized,
Further, there may be mentioned those obtained by adding an alkali agent (for example, sodium carbonate, diethanolamine, sodium hydroxide, etc.), or simply water (tap water, pure water, distilled water, etc.).

Further, a dye such as crystal violet, Victoria Pure Blue, Astrazone Red or the like is added to a developing solution, and the image area can be dyed simultaneously with the development. The development can be performed by a known method, for example, by rubbing the plate surface with a developing pad containing the above-described developer, or rubbing the developer with the developer brush in water after pouring the developer onto the plate surface. The developer can be developed at any temperature, but is preferably from 10C to 50C. As a result, the ink repellent layer in the developing portion is removed, and that portion becomes the ink receiving portion.
The printing plate thus obtained can be detected by dyeing the exposed image portion with a dye solution in order to confirm the image forming property. When the developer does not contain a dye for dyeing the exposed image portion, it is treated with the dye after development. By soaking the dye solution into a soft pad and rubbing the image part lightly, only the exposed image part of the photosensitive layer is dyed,
Thus, it can be confirmed that the development is sufficiently performed up to the highlight portion. As the dyeing solution, one or more selected from water-soluble disperse dyes, acid dyes and basic dyes may be used alone or as a mixture of two or more of water, alcohols, ketones and ethers. What is dissolved or dispersed is used. Carboxylic acids, amines, surfactants, dyeing aids,
It is also effective to add an antifoaming agent or the like. The printing plate dyed with the dyeing solution is preferably washed with water and then dried, whereby the stickiness of the printing plate surface can be suppressed and the handling of the printing plate can be improved. When the plates thus processed are stacked and stored, it is preferable to insert and insert a slip sheet to protect the plates. The above-described development and dyeing, or subsequent washing and drying, are preferably performed by an automatic processor. A preferable example of such an automatic processor is described in JP-A-2-22661.

[0020]

The waterless lithographic printing plate of the present invention is excellent in background stain resistance and printing durability, and the peeling of the silicone rubber layer due to pressure desensitization at the edge of the original film is remarkably improved.

[0021]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Examples 1 to 10, Comparative Examples 1 to 3 (Primer layer) 0.3 mm thick JI degreased by a usual method
An A1050 material aluminum plate is made of KBM603 (manufactured by Shin-Etsu Chemical Co., Ltd.) 1% as an aminosilane coupling agent.
After being immersed in the aqueous solution, it was dried at room temperature. The primer layer described below was applied on this aluminum plate so as to have a dry weight of 4 g / m ^2, and dried by heating at 140 ° C. for 2 minutes. Samprene IB1700D (manufactured by Sanyo Kasei Co., Ltd.) 10 parts by weight Hexafluorophosphate of polycondensation product of p-diazodiphenylamine and 0.1 part by weight of paraformaldehyde 0.1 part by weight of TiO ₂ Defenser 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, FT261V UDNS ULTRA-PLUS FLIPTO manufactured by Nuark
Exposure was performed 20 counts using a P PLATE MAKER vacuum exposure machine.

(Photosensitive Layer) A photopolymerizable photosensitive solution having the following composition was dried on an aluminum plate coated with the primer layer by a dry weight of 4%.
g / m ² and dried at 100 ° C. for 1 minute.・ Polyurethane resin [isophorone diisocyanate / polyester (adipic acid / 1,4-butanediol / 2,2-dimethylpropane-1,3-diol) / isophoronediamine] 1.5 parts by weight ・ A-600 (Shin Nakamura Chemical) 0.5 parts by weight ・ 1 mol of xylylenediamine / 4 mol of glycidyl methacrylate 1.3 parts by weight ・ 0.35 parts by weight of ethyl Michler's ketone ・ 0.10 parts by weight of 2-chlorothioxanthone ・Naphthalene sulfonate of Victoria Pure Blue BOH 0.01 parts by weight ・ Defenser MCF323 (manufactured by Dainippon Ink and Chemicals, Inc.) 0.03 parts by weight ・ Methyl ethyl ketone 10 parts by weight ・ Propylene glycol methyl ether 25 parts by weight (silicone rubber Layer) Dry the following silicone rubber composition solution on the photopolymerizable photosensitive layer. It was applied in a weight 2 g / m ^2, and dried 140 ° C. 2 min. Base polymer as a polysiloxane CH ₂ showing the chain length l in Table 1 = CH- as _{(Si (CH 3) 2 -O} ) l -Si (CH 3) 2 -CH = CH 2 Total 9 parts by weight crosslinking agent Hydrogen polysiloxane (CH ₃ ) ₃ SiO- (SiH (CH ₃ ) -O) _m- (Si (CH ₃ ) ₂ -O) _n -Si (CH ₃ ) ₃ X parts by weight The amount of the hydrogen polysiloxane was determined so that the Si-H group was 10 times the vinyl group of the alkenyl polysiloxane.・ 0.5 parts by weight of polydimethylsiloxane (degree of polymerization: about 8,000) ・ 0.2 parts by weight of olefin-chloroplatinic acid ・ 0.3 parts by weight of inhibitor ・ 140 parts by weight of Isopar G (manufactured by Esso Chemical Co., Ltd.) On the surface of the silicone rubber layer obtained as described above, a single-sided matted biaxially oriented polypropylene film having a thickness of 9 μm was laminated so that the non-matted surface was in contact with the silicone rubber layer. A printing plate was obtained.

[0023]

[Table 1] ─────────────────────────────── Amount of base polymer added Crosslinker copolymer chain length Plate ──── ───────────────────── No. l = 260 l = 500 l = 700 l = 1300 mn ───────────── ────────────────── Example 1-81 1-80 Example 2-72 2-80 Example 3-63 3-80 Example 4-5 4-80 Example 5-7 2-200 Example 6-7 2-400 Example 7-7 2-10 10 Example 8 16 2-80 Example 9-7 11 180 Implementation Example 10 16 1 18 0 ──────────────────────────────── Comparative Example 1-9--80 Comparative Example 2-7 2-5 15 Comparative Example 3--9-80 ────────────────────────────────

Each of these printing plates (600 mm × 450 mm) has
Positive film with a halftone image of 00 lines / inch (45
0mm x 300mm, thickness 100μ)
After exposing for 30 counts using a FT261V UDNS ULTRA-PLUS FLIPTOP PLATE MAKER vacuum exposure machine, the laminate film was peeled off. While immersing the plate in 35 ° C water,
After rubbing with a developing pad to remove the unexposed portion of the silicone rubber layer, it was dyed with a dyeing solution having the following composition to obtain a waterless planographic printing plate precursor. (Staining solution) ・ 0.1 parts by weight of crystal violet ・ 15 parts by weight of diethylene glycol monomethyl ether ・ 85 parts by weight of pure water Next, using these plates, the Toyo Ink was used on a Heidelberg GTO printing machine with the dampening water supply device removed. Made TOY
O KING ULTRA TUK Aqualess G black ink printing, non-image area background stain resistance (ink temperature in the printing machine is 35 ° C), non-image area silicone rubber layer is destroyed, and printed matter becomes dirty. Up to the number of printed sheets (printing durability) and peeling of the silicone rubber layer (film edge) due to pressure desensitization of the original film edge.
Table 2 shows the evaluation results.

[0025]

[Table 2] ────────────────────────────────── Plate No. Ground resistance ^{* 1)} Printing durability Force (10,000 sheets) Film edge ^{* 2)} ────────────────────────────────── Example 1 A 15 A Example 2 A 15 A Example 3 A 14 A Example 4 A 14 A Example 5 A 15 A Example 6 A 15 A Example 7 A 13 AB Example B A 8 A 14 A Example 9 A 14 A Example 10 A 14 A 比較 Comparative Example 1 C 15 A Comparative Example 2 B 12 C Comparative Example 3 A 8 B to C ────────────────────────────────── * 1) A: Absolutely Not dirty B: Almost dirty C: Slightly dirty * 2) Mud edge silicone peeling A: No peeling B: Slight peeling C: Peeling From Table 2, it can be seen that the waterless planographic printing plate of the present invention is a printing plate with good ground stain resistance, printing durability and film edge. Recognize.

Example 11 (Primer layer) A primer layer having the same composition as in Examples 1 to 10 was dried at 3 g / m ² on a 0.24 mm thick aluminum substrate of JIS A1050, which was degreased and silicate treated by a usual method. And dried by heating at 130 ° C. for 2 minutes. Thereafter, exposure was performed in the same manner as in Examples 1 to 10. And (photosensitive layer) is coated on one minute heat dried at 120 ° C. As the photopolymerizable photosensitive solution having the following composition to the primer layer coated aluminum plates on the the dry weight 3 g / m ^2. 1.5 parts by weight of polyurethane resin [isophorone diisocyanate / polyester (adipic acid / 1,4-butanediol / ethylene glycol) / isophorone diamine] 0.3 parts by weight of SARTOMER 9035 (Somar Co., Ltd.) 400) 0.05 parts by weight ・ 1 mol of m-xylylenediamine / 4 mol of glycidyl methacrylate 1.5 parts by weight ・ 0.4 parts by weight of ethyl Michler's ketone ・ 0.05 parts by weight of 2,4-diethylthioxanthone Parts: 9-fluorenone 0.05 parts by weight Eisen Victoria Blue BHconc (manufactured by Hodogaya Chemical Industry Co., Ltd.) 0.01 parts by weight Fluorinated surfactant (MegaFac F177: manufactured by Dainippon Ink and Chemicals, Inc.) ) 0.01 parts by weight ・ Methyl ethyl ketone 20 parts by weight ・ Propylene glycol mono Chirueteru 20 parts by weight

(Silicone Rubber Layer) The following silicone rubber composition was dried on the photopolymerizable photosensitive layer at a dry weight of 1.8 g / m ^2.
And dried by heating at 140 ° C. for 2 minutes. As a base polymer, the following polysiloxane CH ₂ = CH- (Si (CH ₃ ) ₂ -O) ₁ -Si (CH ₃ ) ₂ -CH = CH ₂ l = 500 8 parts by weight l = 700 1 part by weight As a crosslinking agent, the following hydrogen polysiloxane (CH ₃ ) ₃ SiO- (SiH (CH ₃ ) -0) ₈ -Si (CH ₃ ) ₃ 0.4 parts by weight ・ Polydimethylsiloxane (degree of polymerization: about 8,000 0.5 parts by weight ・ (CH ₃ ) ₃ SiO- (Si (CH ₃ ) ₂ -O) _p- (Si (CH ₃ ) (CH ₂ -CH (CH ₃ ) -C ₆ H ₅ ) -O) _q- Si (CH ₃ ) ₃ p: q = 75: 25 Mw = about 2 × 10 ⁴ 0.05 parts by weight ・ Olefin-chloroplatinic acid 0.1 part by weight ・ Control agent 0.1 part by weight ・ Isoper G ( Esso Chemical Co., Ltd.) 100 parts by weight PE on the surface of the silicone rubber layer obtained as described above, having a thickness of 6 μm and having a matte surface for improving vacuum adhesion.
The T film was laminated so that the non-matted surface was in contact with the silicone rubber layer to obtain a waterless planographic printing plate of the present invention. This printing plate was exposed, developed, and dyed in the same manner as in Examples 1 to 10, and as a result of printing, a waterless planographic printing plate excellent in background dirt A rank, printing durability 150,000 sheets, and film edge A rank was obtained. Was done.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Yoshihiko Urabe 4,000 Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Prefecture Inside Fuji Photo Film Co., Ltd. (72) Inventor Izumi Hirano 4,000 Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Fuji Fuji Photo Film Stock In-company (72) Inventor Toshio Ohba 2-6-1, Otemachi, Chiyoda-ku, Tokyo Shin-Etsu Chemical Co., Ltd. (56) References JP-A-4-68353 (JP, A) JP-A-2-79852 ( JP, A) JP-A-3-276155 (JP, A)

Claims (1)

(57) [Claims] In a photosensitive lithographic printing plate requiring no fountain solution, a photosensitive layer and a silicone rubber layer are laminated on a support in this order, the silicone rubber layer comprises (a) silicon atoms in one molecule. A — (Si (R ¹ ) (R ² ) —O) ₁ — group of a polysiloxane having at least two directly bonded alkenyl groups (wherein R ¹ and R ² are an alkyl group, an aryl group, an aralkyl group,
Represents a vinyl group or a halogenated hydrocarbon group. Where R
¹ , 70% or more of R ² is a methyl group. ), The average number of repetitions l is (i) 50 to 95% by weight of a polysiloxane having 100 ≦ l ≦ 500, and (ii) 5 to 50% by weight of a polysiloxane having 700 ≦ l ≦ 10000 ((i) + ( ii) = 100% by weight) and (b) a hydrogen polysiloxane of the following general formula (I): R ³ —Si (R ⁴ ) ₂ —O— (SiH (R ⁴ ) —O) _m — ( Si (R ⁴ ) ₂ -O) _n -Si (R ⁴ ) ₂ -R ³ (I) wherein R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents an alkyl group, an aryl group, an aralkyl group or Represents a vinyl group, which may be the same or different, provided that
More than 70% of R ⁴ is a methyl group. Also, m + n = 4
１００100, and n / m = 0０〜1. A) a lithographic printing plate requiring no dampening solution, characterized in that the lithographic printing plate is crosslinked by an addition reaction.