JPH02235064A - Damping-waterless photosensitive planographic printing plate - Google Patents

Abstract

PURPOSE:To enhance the adhesiveness between a photosensitive resin layer and a primer layer by adding a specific ratio of a diazo resin to the photosensitive resin layer. CONSTITUTION:This printing plate is formed by successively laminating the primer layer, the photosensitive resin layer (A) and a silicone rubber layer on a substrate, such as Al plate. A monomer or oligomer having >=1 photopolymerizable or photocrosslinkable and olefinic unsatd. double bond groups and a high-polymer compd. which is to be added at need and has film formability, as well as a photopolymn. initiator and the diazo resin (a) are incorporated into the layer A. The content of the component (a) is specified to 0.01 to 10wt.% by the weight of the layer A. A PF6 salt of the condensate of p-diazophenyl amine/formaldehyde is usable for the component (a).

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a photosensitive lithographic printing plate that does not require dampening water and is capable of printing without using dampening water.

<Prior Art and Problems to be Solved> Various types of photosensitive planographic printing plates that do not require dampening water have been proposed for performing planographic printing without using dampening water. Among these, those in which a photosensitive resin layer and a silicone rubber layer are sequentially coated on the base plate have extremely superior performance, and are described in, for example, Japanese Patent Publication No. 54-26923 and Japanese Patent Publication No. 55-22781. I can list things that I have.

The silicone rubber layer used in these photosensitive lithographic printing plates that do not require dampening water is usually made of a high molecular weight polymer whose main skeleton is polysiloxane, which is partially cross-linked using a cross-linking agent. On the other hand, as the photosensitive resin layer, in the case of a positive planographic printing plate, a photopolymerizable photosensitive resin layer, a photodimerization type photosensitive resin layer, or a diazo type photosensitive resin layer, which is cured by exposure to light, have been used. The image forming method for photosensitive lithographic printing plates having these layer structures generally involves curing the photosensitive resin layer by exposure to light, and in some cases, photo-adhering it at the interface with the upper silicone rubber layer. , a non-image area made of a silicone rubber layer is formed by firmly bonding both glabellar spaces and preventing penetration by the developer and accompanying elution of the photosensitive resin layer. On the other hand, in the image area, a developer is penetrated through the silicone rubber layer to dissolve part or all of the uncured photosensitive resin layer, and then the silicone rubber layer thereon is removed by physical force. It is formed by. An image is formed in this manner, and in order to improve the image forming properties, it is important that the photosensitive resin layer and the substrate are firmly bonded. For this purpose, a brimer layer is usually provided between the photosensitive resin layer and the substrate. However, since the primer layer has various roles in addition to adhesion to the photosensitive resin layer, its adhesive strength has not always been sufficient. In particular, when the photosensitive resin layer is a photopolymerizable photosensitive resin material or a photodimerizable photosensitive resin layer, the adhesion strength is insufficient, resulting in problems such as insufficient image forming properties. Therefore, an object of the present invention is to provide a photosensitive lithographic printing plate that has excellent image forming properties and does not require dampening water. <Means for Solving the Problems> As a result of intensive studies to achieve the above object, the present inventors have developed a dampener comprising a layer of brimmer, a photosensitive resin layer and a silicone rubber layer laminated in this order on a substrate. By adding diazo resin to the photosensitive resin layer in water-free photosensitive lithographic printing plates, adhesion between the primer layer and the primer layer is improved, and dampening water-free photosensitive lithographic printing plates with excellent image area formation properties. The inventors have discovered that this can be obtained, and have arrived at the present invention.

That is, the present invention provides a photosensitive lithographic printing plate that does not require dampening water and is formed by sequentially laminating a brimer layer, a photosensitive resin layer, and a silicone rubber layer on a substrate, in which the photosensitive layer has the following components: +1) At least 1 (2) A polymeric compound having a film-forming ability, which is used as necessary, and (3) Photopolymerization A dampening water-free photosensitive lithographic printing comprising: an initiator; This is the edition. The lithographic printing plate of the present invention, which does not require dampening water, must have enough flexibility to be able to run on a normal printing machine, and must be able to withstand the load applied during printing. Therefore, typical substrates include coated paper, metal plates such as aluminum, plastic films such as polyethylene terephthalate, rubber, and composites of these. Various primer layers can be used to improve the adhesion between the substrate and the photosensitive resin layer, to prevent halation, and to improve the dyeing and printing characteristics of images. For example, JP-A-60-22
903, various photosensitive polymers are exposed to light and cured before laminating a photosensitive resin layer, and epoxy resins disclosed in JP-A-62-50760 are heat-cured. 13315/1986
Examples include hardened gelatin disclosed in No. 1 and hardened casein. Furthermore, for the purpose of softening the primer layer, polyurethane, polyamide, styrene/butadiene rubber, carpoxy-modified styrene/butadiene rubber, acrid nitrile/butadiene rubber, carvonine, etc., whose glass transition temperature is below room temperature, is added to the primer layer. Polymers such as acid-modified nitrile/butadiene rubber, polyisobrene, acrylate rubber, polyethylene, chlorinated polyethylene, and chlorinated polypropylene may be added. The addition ratio is arbitrary, and the primer layer may be formed using only the additive as long as it is within the range that allows the formation of a film layer. In addition, in accordance with the above-mentioned purpose, these brimer layers contain dyes, PLL indicators, print-out agents, photopolymerization initiators, adhesion aids (e.g., polymerizable monomers, diazo resins, silane coupling agents, titanate coupling agents). It is also possible to contain additives such as white pigments and silica powder.Generally, the coating amount of one layer of brimmer is 2 to 20 g/m' in terms of dry weight.

The photosensitive resin layer used in the present invention includes (1) a monomer or oligomer having at least one photopolymerizable or photocrosslinkable olefinic unsaturated double bond group;
2) A photopolymerizable photosensitive resin layer consisting of a polymer compound having film-forming ability, (3) a photopolymerization initiator, and (4) a diazo resin, if necessary. The above ingredients (1) to (
In the photosensitive resin layer containing 4), a compound in which components (1) and (2) are bonded, that is, at least one photopolymerizable or photocrosslinkable and olefinic unsaturated double compound in the side chain. A photosensitive resin layer containing a polymer compound having a bonding group and film-forming ability is also suitable for use in the present invention. Also,. A photosensitive resin layer in which a monomer or oligomer of component (1) is further added to a compound in which components (1) and (2) are combined is more suitable, but the present invention is not limited thereto. do not have.

Monomers or oligomers having at least one photopolymerizable olefinically unsaturated double bond group include polyethylene glycol mono(meth)acrylate, polybrobylene glycol mono(meth)acrylate, phenoxyethyl(meth)acrylate, - Monofunctional acrylates and methacrylates such as (meth)acryloxyethyl water phthalate and 2-(meth)acryloxyethyl hydrogen succinate; polyethylene glycol di(meth)
Acgurate, trimethylolethane tri(meth)acrylate, neobentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, diventaerythritol hexa(meth)acrylate, Heisandi All-di(meth)acrylate, trimethylolpropane tri(acryloyloxybutyl)ether, tri(acryloyloxyethyl)isocyanurate, calcium (meth)acrylate, sodium (meth)acrylate, glycerin, trimethylolethane, etc. 4B-41708, 1973
Urethane acrylates such as those described in JP-A-6034 and JP-A-51-37193;
-64183, Special Publication No. 49-43191, Special Publication No. 5
Polyester acrylates described in each publication of No. 2-30490, polyfunctional acrylates and methacrylates such as epoxy acrylate neck made by reacting epoxy resin and (meth)acrylic acid, N-1 described in U.S. Patent No. 4,540,649 Examples include methylol acrylamide derivatives. Furthermore, Japan Adhesive Association Journal Vol. 2
0, Na7, pages 300 to 308, those introduced as photocurable monomers and oligomers can also be used. The amount of these monomers and oligomers is generally 70 to 1% by weight, preferably 50 to 3% by weight of the total photosensitive resin layer.
It is. (2): Polymer compounds with film-forming ability that can be used as necessary in the present invention include methacrylic acid copolymers, acrylic acid copolymers, crotonic acid copolymers, and maleic acid copolymers. , partially esterified maleic acid copolymer, acidic cellulose fB, polyvinylpyrrolidone, polyethylene oxide, alcohol-soluble nylon, polyester, unsaturated polyester, polyurethane, polystyrene, eboxy resin, phenoxy resin, polyvinyl butyral, polyvinyl formal, polyvinyl chloride Examples include polyvinyl alcohol, partially acetalized polyvinyl alcohol, water-soluble nylon, water-soluble urethane, gelatin, and water-soluble cellulose derivatives. A polymer compound in which (11 and (2) are incorporated) A polymer compound in which the above components Tl) and (2) are bonded, that is, at least one photopolymerizable or photocrosslinkable and olefinic unsaturated dihydrogen compound in the side chain. Examples of the polymer compound having a heavy bond group include allyl (meth)acrylate/(meth)acrylate as described in JP-A No. 59-53836;
Acrylic acid/other addition-polymerizable vinyl monomer copolymers as required, and alkali metal salts or amine salts thereof; Hydroxyethyl (meth)acrylate/(meth)acrylic described in Japanese Patent Publication No. 59-45979 Acid/alkyl (meth)acrylate copolymer and its alkali metal salt or amine salt are reacted with (meth)acrylic acid chloride; Polymers with pentaerythritol triacrylate added by half-esterification and their alkali metal salts or amine salts; styrene/maleic anhydride copolymers with monohydroxyalkyl (meth)acrylates, polyethylene glycol mono(meth)acrylates, etc. Polypropylene glycol mono (meth)acrylate added by half-esterification and its alkali metal salts and amine salts; (meth)
Acrylic acid copolymers and crotonic acid copolymers in which part of the carboxylic acid is reacted with glycidyl (meth)acrylate, and their alkali metal salts and amine salts; hydroxyalkyl (meth)acrylate copolymers, polyvinyl formal, Polyvinyl butyral reacted with maleic anhydride or itaconic anhydride, and their alkali metal salts and amine salts; hydroxyalkyl (meth)acrylates/
(meth)acrylic acid copolymer with 2,4-tolylene diisocyanate/hydroxyalkyl (meth)acrylate 1
-=1/1 adducts and their alkali metal salts and amine salts; a part of the (meth)acrylic acid copolymer described in JP-A No. 59-53836 is converted into allylglycyl ether and its alkali metal salt or amine salt; Vinyl (meth)acrylate/(
Meth)acrylic acid copolymer and its alkali metal salt or amine salt: (meth)allyl acrylate/sodium styrene sulfonate copolymer; (meth)vinyl acrylate/sodium styrene sulfonate copolymer, (meth)
Allyl acrylate/acrylamide 1.1-sodium dimethylethylene sulfonate copolymer, vinyl (meth)acrylate/acrylamide 1.1-sodium dimethyl ethylene sulfonate copolymer, 2-allyloxyethyl methacrylate/methacrylic acid Copolymer, 2-
Examples include allyloxyethyl methacrylate/2-methacryloxyethyl hydrogen succinate copolymer. The amount of the above-mentioned polymer compound is generally 30% in the total photosensitive resin layer.
-99% by weight, preferably 50-97% by weight. (3): Heavy A1 As a photopolymerization initiator used in the present invention, US Pat.
, 367.660, U.S. Patent No. 2.367.66.
1 and 2.367.670, U.S. Pat. No. 2.448.82
No. 8, U.S. Pat. No. 2,722,512, Akira I! α-mono-hydrocarbon-substituted aromatic acytoyne compounds disclosed in Book II; polynuclear quinone compounds disclosed in U.S. Pat. No. 3,046,127 and U.S. Pat. US Patent No. 3
．． 1-Rearylimidazole dimer/p-aminophenyl ketone combination disclosed in US Pat. No. 549,367, penzothiazole compounds disclosed in US Pat. No. 3,870,524, US Pat. Penzothiazole compounds/trihalomethyl-s-}riazine compounds disclosed in U.S. Pat. No. 4,239,850 and acridine and phenazine compounds disclosed in U.S. Pat. Oxadiazole compounds disclosed in Patent No. 4.212.970, U.S. Patent No. 3,954.475, JP-A-53-133428, U.S. Patent No. 4.189
．． No. 323, JP-A-60-105667, JP-A-62
-58241, Toriyakuchi methyl-s-} having a chromophore group disclosed in Japanese Patent Application No. 61-227489
Examples include riazine compounds, penzophenone group-containing beroxy ester compounds disclosed in JP-A-59-197401 and JP-A-60-76503.

The amount of these photosensitive initiators added is 0.1/20%, more preferably 1 to 10% based on the total photosensitive resin layer.
It is. }(41:Diazo}6 The diazo resins added to improve the adhesion between the photosensitive resin layer and the primer layer include (A) 4-diazodiphenylamine, l-diazo4-N, N-dimethylaminobenzene, l-diazo-4-N,N-diethylaminobenzene, ■-diazo-4-N-ethyl-N-hydroxyethylaminobenzene, !-diazo-4-N-methyl-N-hydroxyethylaminobenzene, 1-Diazo 2,5-jethoxy-4-penzoylaminobenzene, 1-diazo 4-N-penzylaminobenzene, 1-
Diazo-4-N,N-dimethylaminobenzene, l-diazo4-morpholinobenzene, l-diazo2.5
-dimethoxy-4-p-tolylmercaptobenzene, 1
-diazo-2-ethoxy-4-N,N-dimethylaminobenzene, p-diazodimethylaniline, l-diazo2,5-dibutoxy-4-morpholinobenzene, l
Diazo-2,5-jethoxy-4-morpholinobenzene, l-diazo2,5-dimethoxy-4-morpholinobenzene, l-diazo2,5-diethoxy-4-morpholinobenzene, ■-diazo2,5- Jetoxy-4-p-tolylmercabutobenzene, I-diazo 3
-Ethoxy4-N-methyl-N-pendylaminobenzene, 1-diazo3-chloro-4N,N-jethylaminobenzene, 1-diazo3-methyl-4-pyro1r
Dinobenzene, l-diazo-2-chloro-4-N,N-
Dimethylamino-5-methoxyhenzene, l-diazo3-methoxy4-virolidinobenzene, 3-methoxy-4-diazodiphenylamine, 3-ethoxy-4-
Diazodiphenylamine, 3-(n-broboxy)-4
-Diazodiphenylamine, 3-(isobropoxy)-
A diazo monomer such as 4-diazodiphenylamine and (
B) With a condensing agent such as formaldehyde, acetaldehyde, blobionaldehyde, butyraldehyde, isobutyraldehyde, benzaldehyde, etc., respectively in l:1 to X:
O. S, preferably 1:0.8 to t:o. A condensate obtained by condensation in a conventional manner at a molar ratio of e, an anion,
The reaction products of Examples of anions include boron tetrafluoride, phosphoric hexafluoride, triisobrobylnaphthalenesulfonic acid, 5-nitroorthotoluenesulfonic acid, 5-sulfosalicylic acid, 2.5-dimethylbenzenesulfonic acid, 2.4.6 -}limethylbenzenesulfonic acid, 2-nitrobenzenesulfonic acid, 3-chlorobenzenesulfonic acid, 3-promobenzenesulfonic acid, 2
-fluorocabrylnaphthalenesulfonic acid, dodecylbenzenesulfonic acid, 1-naphthol-5-sulfonic acid,
Examples include 2-methoxy-4-hydroxy-5-penzoylbenzenesulfonic acid, and hypotoluenesulfonic acid. Among these, phosphorus hexafluoride and alkyl aromatic sulfonic acids such as triisobrobylnaphthalenesulfonic acid and 2,5-dimethylbenzenesulfonic acid are particularly suitable. The amount of the diazo resin added to the entire photosensitive resin layer is 0.01 to 10% by weight, more preferably 0.03 to 3% by weight.

Other components added to the photosensitive resin layer It is preferable to add a thermal polymerization inhibitor to the photosensitive resin layer. For example, hydroquinone, p-methoxyphenol, di-t
-Butyl-p-cresonopebiroganoKt-butylcatechol, penzoquinone, 4,4'-thiobis(3-
methyl-6-t-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol),
Examples include 2-mercabutobenzimidazole. Further, dyes or pigments may be added for the purpose of coloring the photosensitive resin layer, and a PLL indicator or leuco dye may be added as a printing-out agent. In addition, a small amount of silicone compounds such as polydimethylsiloxane, methylstyrene-modified polydimethylsiloxane, olefin-modified polydimethylsiloxane, polyether-modified polydimethylsiloxane, silane coupling agent, silicone diacrylate, silicone dimethacrylate, etc. are contained in the photosensitive resin layer. may be added. Furthermore, in order to improve coating suitability, a fluorine-based surfactant or a fluorine-based surface alignment agent may be added. The amount of these additives added is usually 10% by weight or less based on the total photosensitive resin layer. Furthermore, in order to strengthen the adhesion with the silicone rubber layer if necessary, silica powder or hydrophobic silica powder whose surface has been treated with a (meth)acryloyl group or allyl group-containing silane coupling agent is applied to the entire photosensitive resin layer. It may be added in an amount of 50% by weight or less. For the photosensitive resin layer as described above, the composition for the photosensitive resin layer is, for example, 2-methoxyethanol, 2-methoxyethyl acetate, methyl lactate, ethyl lactate, propylene glycol monomethyl ether, brobylene glycol monomethyl ether acetate, methanol. , dissolved in a suitable solvent such as ethanol, methyl ethyl ketone, water, etc. alone or in a mixed solvent of an appropriate combination thereof, and the weight after drying is about 0.1-1.
0 g/m'', more preferably 0.5-5 g/m'
It is formed by coating it on a substrate so that it has a coating amount of , and drying it.

The silicone rubber layer preferably used in the present invention is a linear or partially crosslinked polydiorganosiloxane having the following repeating units.

2, R represents an alkyl group, an aryl group, an alkenyl group, or a combination of these groups, and these groups include a halogen atom, an amine group, a hydroxy group, an alkoxy group, an aryloxy group, a (meth)acryloxy A functional group such as a group or a thiol group may be present. The silicone rubber layer may be coated with adhesion aids such as silica, calcium carbonate, titanium oxide, or other non-precipitated powders, the silane coupling agent, titanate coupling agent, or aluminum coupling agent, if necessary. It is also possible to add a light initiator. A high molecular weight polymer whose main skeleton is the above-mentioned polysiloxane (
Polysiloxane, which has a molecular weight of several tens to hundreds of thousands and has a functional group at the end, is used as a raw material for silicone rubber.
This is crosslinked and cured by the following method to form a silicone rubber layer.

Specifically, the polysiloxane having a hydroxyl group at both ends or at one end is mixed with a silane-based crosslinking agent represented by the following general 2, and if necessary, an organometallic compound such as an organotin compound is mixed. It is formed by adding a catalyst such as a compound, an inorganic acid, or an amine, and heating polysiloxane and a silane crosslinking agent, or by condensation curing at room temperature. R IISi X a-m Here, n is an integer of 1 to 3, R is the same substituent as R shown above, and X represents a ZIA group such as -OH, -OR''. Here, R2 and R3 have the same meaning as R described above, and R2 and R'' may be the same or different. Furthermore, Ac represents an acetyl group. The silicone rubber layer may also be formed by condensation curing of an organoborisiloxane having a hydroxyl group at the end, a hydrogen polysiloxane crosslinking agent, and, if necessary, the above-mentioned silane crosslinking agent. Also useful is an addition-type silicone rubber layer crosslinked by an addition reaction between a StH group and a C H =C H group. Additive silicone rubber layers have the advantage that they are relatively unaffected by humidity during curing, can be crosslinked at high speed, and can easily obtain certain physical properties. In the case of a reduction type silicone rubber layer, if carboxylic acid is present in the photosensitive resin layer, curing failure may occur depending on the crosslinking agent used, whereas with an addition type, even if carboxylic acid is present, curing is insufficient. Hardens. In this way, with the addition type, since carboxylic acid can be present in the photosensitive resin layer, it can be developed with a developer mainly composed of water or alkaline water, making it possible to easily design photosensitive printing plates. be. The addition type silicone rubber layer used here contains polyvalent hydrogen organoborisiloxane and two or more monocarbons in one molecule.
It is obtained by reaction with a polysiloxane compound having one H = C H bond, and preferably contains the following components: (l) a small number of alkenyl groups (preferably vinyl groups) directly bonded to a silicon atom in one molecule; <<100 parts by weight of an organoborisiloxane having both 2 bonds (2) 0.1-1 organohydrogenpolysiloxane having at least two 95i1{bonds in one molecule
000 parts by weight (3) Addition catalyst o. This is a composition obtained by curing and crosslinking a composition consisting of ~10 parts by weight. Ingredient fl
The alkenyl group in ) may be located either at the end or in the middle of the molecular chain, and organic groups other than the alkenyl group include substituted or unsubstituted alkyl groups and ryol groups. Ingredients (1
1 may contain a hydroxyl group. Ingredient (2)
reacts with component (1) to form a silicone rubber layer, but also plays the role of providing adhesiveness to the photoresist resin layer.
The hydrogen group in component (2) may be located either at the end or in the center of the molecular chain, and the organic groups other than hydrogen are selected from those similar to component (1). MUM of component (11 and component (2))
In order to improve ink repulsion, it is preferable that 60% or more of the groups are methyl groups. Component (1) and component (
The molecular structure of 2) may be linear, cyclic, or branched, and the molecular weight of at least one of them is 1. o o o
It is preferable from the viewpoint of rubber physical properties that the component (1
It is preferred that the molecular weight of 1 exceeds 1,000.

Component (1) is exemplified by α,ω-divinylpolydimethylsiloxane, (methylvinylsiloxane)(dimethylsiloxane) copolymer having methyl groups at both ends, and component (2) is exemplified by Examples include polydimethylsiloxane, α,ω-dimethylpolymethylhydrogensiloxane, (methylhydrogensiloxane)(dimethylsiloxane) copolymer with methyl groups at both ends, and cyclic polymethylhydrogensiloxane. The addition catalyst for component (3) can be arbitrarily selected from known ones, but platinum-based compounds are particularly preferred, and examples include simple platinum, platinum chloride, chloroplatinic acid, and olefin-coordinated platinum. For the purpose of controlling the cure rate of these compositions, organopolysiloxanes containing vinyl groups, such as tetracyclo(methylvinyl)siloxane, alcohols containing carbon-carbon triple bonds, acetone, methyl ethyl ketone, methanol, ethanol, propylene, etc. It is also possible to add crosslinking inhibitors such as glycol monomethyl ether. In these compositions, an addition reaction occurs and curing begins when the three components are mixed, but the curing rate is characterized by rapidly increasing as the reaction temperature increases. Therefore, in order to lengthen the pot life of the composition until it becomes a rubber and shorten the curing time on the photosensitive resin layer, the curing conditions for the composition are set within a range that does not change the characteristics of the substrate and the photosensitive resin layer. It is preferable to maintain the temperature at a high temperature until completely cured in order to maintain the stability of the adhesive force with the photosensitive resin layer. In addition to these compositions, known adhesion promoters such as alkenyltrialkoxysilanes may be added, and organopolysiloxanes containing hydroxyl groups and silanes containing hydrolyzable functional groups ( or siloxane) may be added. Further, in order to improve the rubber strength, a known filler such as silica may be added. The silicone rubber layer in the present invention serves as a printing ink repellent layer, and if the thickness is small, there are problems such as a decrease in ink repellency and the possibility of scratches, while if the thickness is large, developability will be poor. From the point, the thickness is 0.
5 to 5 microns is preferred. In the photosensitive lithographic printing plate that does not require dampening water as described here,
Various silicone rubber layers may be further coated on the silicone rubber layer. In addition, in order to increase the adhesive strength between the photosensitive layer and the silicone rubber layer, or to prevent poisoning of the catalyst in the silicone rubber composition, an adhesive layer is provided between the photosensitive resin layer and the silicone rubber layer. It may be provided. Furthermore, to protect the surface of the silicone rubber layer,
It may be laminated with a transparent film such as polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polyvinylalconope, polyethylene terephthalate, cellophane, etc., or coated with a polymer.

The photosensitive lithographic printing plate that does not require dampening water according to the present invention includes a developer that can dissolve or swell part or all of the photosensitive resin layer in the image area (unexposed B) after frosting through the transparent original image.
Alternatively, it is developed with a developer capable of swelling the silicone rubber layer. In this case, there are cases in which the photosensitive resin layer in the image area and the silicone rubber layer thereon are removed, and cases in which only the silicone rubber layer in the image area is removed, and this can be controlled by the strength of the developer. be able to.

As the developer used in the present invention, those known as developers for photosensitive lithographic printing plates that do not require dampening water can be used. For example, aliphatic hydrocarbons (hexane, hebutane,
'Isobar E, H, G' (trade name of aliphatic hydrocarbons manufactured by Esso Chemical Co., Ltd. or gasoline, kerosene, etc.),
Suitable are aromatic hydrocarbons (toluene, xylene, etc.), halogenated hydrocarbons (triclene, etc.) to which the following polar solvents are added, or polar solvents themselves.

・Alcohols (methanol, probanol, benzyl alcohol, ethylene glycol monophenyl ether, 2-methoxyethanol, 2-ethoxyethanol, carbitol monoethyl ether, carbitol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monoethyl ether) Glycol monomethyl ether, brobylene glycol monoethyl ether, cypropylene glycol monomethyl ether, polyethylene glycol monomethyl ether, propylene glycol, triethylene glycol, tetraethylene glycol》 Ketones (acetone, methyl ethyl ketone), esters (ethyl acetate, methyl lactate, ethyl lactate, lactate ptynopebropylene glycol monomethyl ether acetate, carbitol acetate, dimethyl phthalate, diethyl phthalate) Others (triethyl phosphate, tricresidyl phosphate) In addition, the above organic solvents Adding water to the developer, or making the above organic solvent solubilized in water using a surfactant, etc.
Furthermore, alkaline agents such as sodium carbonate, monoethanolamine, diethanolamine, triethanolamine, sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, sodium borate, etc. are added thereto, or in some cases. can simply use tap water or alkaline water as a developer.

Furthermore, dyes such as crystal violet and astrazone red can be added to the developer to dye the image area at the same time as development.

The development can be carried out by a known method, such as rubbing the printing plate with a developing pad containing a developer as described above, or pouring the developer onto the printing plate and then rubbing it with a developing brush in water. As a result, the silicone rubber layer and photosensitive resin layer in the image area are removed, and the surface of the substrate/plate or brimer layer is exposed, and that part becomes the ink receiving area, or only the silicone rubber layer in the image area is removed. The photosensitive liqueur layer is exposed and that area becomes the ink receiving area.

Effects of the Invention> The photosensitive lithographic printing plate that does not require dampening water according to the present invention has on the substrate,
It has a layer structure in which a single layer of brimmer, a photosensitive anti-glare layer and a silicone rubber layer are laminated in this order, and the photosensitive layer includes:
(1) a monomer or oligomer having at least one photopolymerizable or photocrosslinkable olefinically unsaturated double bond group; (2) a polymer compound having film-forming ability as necessary; (3) Since a composition comprising a photopolymerization initiator and (4) a diazo resin is used, the adhesion between the brimer layer and the photosensitive resin layer is improved, and excellent image forming properties can be obtained.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.

Example 10. 3 Apply the following brimer layer composition solution on a 11101 thick smooth IS material aluminum plate to a dry weight of 10 g/m', and
℃ for 3 minutes to dry and harden the film.

Milk casein 48 parts by weight Glyoxal 40% aqueous solution 5 parts by weight (yellow dyeing l11
) 1.2 weight (Japanese) On the aluminum plate coated with the above-mentioned brimer layer, apply a photosensitive resin layer composition solution having the following composition at a dry weight of 3 g/
m' and dried at 100° C. for 1 minute.

NazCOs T102 2.6 parts by weight 1 part by weight 0H 0.2 parts by weight 1 part by weight Methyl ethyl ketone 10 parts by weight Then, on the photosensitive resin layer, the following composition liquid for silicone rubber layer was applied at a dry weight of 2.0 g/m ', apply to 140
℃ for 2 minutes to obtain a cured silicone rubber layer.

α. ω-divinylpolydimethyl 9 parts by weight Siloxane (degree of polymerization about 700) Borydimethylsiloxane (degree of polymerization about 8,000) 0.5 parts by weight Evil olefin-chloroplatinic acid 0.2 parts by weight Inhibitor
0.15 parts by weight Isobar G (manufactured by Esso Kagaku ■) A 9 μm thick single-sided mapped polypropylene film was laminated on the surface of the silicone rubber layer obtained as above, and photosensitive lithographic printing without the need for dampening water was performed. Got the edition.

This printing plate is overlaid with a body film and vacuum-adhered to the Nuark Co., Ltd. FT26V IJDNS ULTRA-PLIJ.
S FLIP-TOPPLATE! After 30 counts of exposure with JAκεR, the laminate film was peeled off and placed in a developer consisting of 12 parts by weight of benzyl alcohol, 5 parts by weight of sodium isobrobylnaphthalene sulfonate, 1 part by weight of triethanolamine, and 82 parts by weight of water for 1 minute. When the sample was immersed and rubbed with a developing pad, the photosensitive resin layer and silicone rubber layer in the unexposed areas were removed. In this way, a lithographic printing plate that did not require dampening water was obtained, which faithfully reproduced the image of the body film over the entire surface of the printing plate.

As a comparative example, a photosensitive lithographic printing plate that did not require dampening water was prepared using a photosensitive fat layer obtained by removing the diazo resin from the photosensitive resin layer, and when exposed and developed under the same conditions, the photosensitive resin layer and the brimer were removed. Due to insufficient adhesion with the first layer, a printing plate with extremely poor reproducibility of the shards was obtained.

Example 2 On the aluminum substrate coated with the brimer layer used in Example 1, a composition liquid for a photosensitive resin layer having the same composition was applied and dried at 100° C. for 1 minute. The dry coating weight was 3.0 g/m''.

Tricresicyl phosphate 0.3 parts by weight Victoria Biable BOH 0.2 parts by weight 0. 1 part by weight of methanol silica (30% solution) Next, on the photosensitive resin layer, a composition liquid for a silicone rubber layer having the following composition was applied to a dry weight of 2.0 g/m'', It was dried at 140°C for 2 minutes to obtain a cured silicone rubber layer.

CH, CH3H CH
, 1 part by weight Olefin-chloroplatinic acid 0.2 parts by weight Inhibitor 0.15 parts by weight Isopar G (manufactured by Esso Chemical ■) 160 parts by weight One side with a thickness of 9 μm was applied to the surface of the silicone rubber layer obtained as above. A matte polypropylene film was laminated to obtain a photosensitive lithographic printing plate that did not require dampening water.

Exposure and development were carried out in the same manner as in Example 1 to obtain a lithographic printing plate that did not require dampening water and had excellent image forming properties.

As a comparative example, a photosensitive lithographic printing plate that did not require dampening water was prepared using a photosensitive resin layer with the diazo resin removed from the photosensitive resin layer, and when exposed and developed under the same conditions, the photosensitive resin layer and the primer layer were Due to insufficient adhesion to the brimer layer, the photosensitive resin layer peeled off from the brimer layer, making it impossible to form a sufficient image.

Example 3 On an aluminum substrate coated with the brimer layer used in Example 1, a composition solution for a photosensitive resin having the following composition was applied in an amount of 3.5% by dry weight. Apply to 0 g/m', 10
It was dried at 0°C for 1 minute.

Fluorine-based nonionic surfactant 0. 0.2 parts by weight of old weight 10 parts by weight of methyl ethyl ketone A composition solution for a silicone rubber layer having the following composition was applied onto the photosensitive resin layer so that the dry weight was 2 g/m'.
It was dried at 80°C for 5 minutes to obtain a cured silicone rubber layer.

Methyltriacetoxysilane Dibutyltin acetate 0.5 parts by weight 0.02 parts by weight A single-sided matted polyethylene terephthalate film with a thickness of 6.5 μm was laminated on the surface of the silicone rubber layer thus obtained, and a dampening solution was not required. A lithographic printing plate was obtained.

This printing plate was exposed for 30 minutes using the vacuum exposure machine used in Example 1.
Count exposure, then peel off the laminate film,
After immersing it in triethylene glycol at 30°C for 1 minute, the surface was rubbed in water using a developing bat to remove the silicone rubber layer in the unexposed areas. In this way, a lithographic printing plate requiring no dampening water was obtained that faithfully reproduced the image of the positive film over the entire surface of the printing plate.

As a comparative example, when a photosensitive resin layer excluding the diazo resin from the photosensitive resin layer described above was used, the brimmer layer and the photosensitive resin layer were separated during development, and a satisfactory image could not be obtained. .

Procedural amendment 1989 Month Day

Claims (1)

[Claims] A dampening water-free photosensitive lithographic printing plate comprising a primer layer, a photosensitive resin layer and a silicone rubber layer sequentially laminated on a substrate, wherein the photosensitive resin layer has the following components: (1 ) a monomer or oligomer having at least one photopolymerizable or photocrosslinkable olefinically unsaturated double bond group; (2) a polymeric compound having film-forming ability, used as necessary; ( 3) a photopolymerization initiator; and (4) a diazo resin; a dampening solution characterized in that the content of the diazo resin is 0.01 to 10% by weight based on the total photosensitive resin layer. Unnecessary photosensitive lithographic printing plate.