JPH0876368A - Waterless planographic printing original plate - Google Patents

Abstract

PURPOSE: To obtain a waterless planographic printing original plate having excellent image reproducibility and printing durability which can be suitably used for commercial rotary offset printing and newspaper rotary offset printing which require high printing durability. CONSTITUTION: This waterless planographic printing original plate is obtd. by forming a photosensitive layer containing at least a quinonediazide compd. and a binder polymer and an ink-repellent layer on a substrate in this order. As for the tensile characteristics of the photosensitive layer, it has such physical properties as (1) 5 to 50kgf/mm<2> , initial elastic modulus, (2) 0.05-3.0kgf/mm<2> 10% stress and (3) >=10% fracture elongation.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a waterless planographic printing plate, and more particularly to a waterless planographic printing plate having markedly improved printing durability.

[0002]

2. Description of the Related Art Conventionally, various printing plates have been proposed for using a silicone rubber layer as an ink repellent layer and performing lithographic printing without using fountain solution.

For example, as a positive-working photosensitive lithographic printing plate, JP-B-54-26923 or JP-B-56 may be used.
No. 23150, a waterless planographic printing plate in which a photopolymerizable adhesive layer and a silicone rubber layer are laminated on a substrate, and Japanese Patent Publication No. 3-56622 and JP-A 61-153.
A waterless lithographic printing plate in which a photodimerization type photosensitive layer and a silicone rubber layer are laminated on a substrate is proposed in Japanese Patent No. 655, etc.

Further, as a negative type photosensitive lithographic printing plate, a photosensitive layer containing an orthoquinonediazide compound is provided on a substrate of Japanese Patent Publication No. 61-616 and Japanese Patent Publication No. 61-54218, and an adhesive layer is provided thereon. A waterless lithographic printing plate provided with a silicone rubber layer has been proposed as a waterless lithographic printing plate provided with a silicone rubber layer on a photoreleasable photosensitive layer, such as Japanese Patent Publication No. 61-54222. It is known to have excellent performance. Among them, Japanese Patent Publication No. 61-52222 particularly discloses photo-exfoliation in which a partial esterified product of naphthoquinone-1,2-diazide-5-sulfonic acid chloride and phenol novolac resin is crosslinked on a substrate with a polyfunctional isocyanate. There is disclosed a negative type waterless planographic printing plate provided with a photosensitive layer and a silicone rubber layer as an ink repellent layer thereon.

However, in these photosensitive lithographic printing plates, the photosensitive layer is relatively hard and brittle, and therefore, during offset printing,
It is easy to be damaged by the stress applied to the plate surface, and as the number of printed sheets increases, the photosensitive layer below the silicone rubber layer in the non-image area will be damaged, and this will spread to the silicone rubber layer and the image reproducibility will deteriorate. Occurs. As a result, it appears as a problem of insufficient printing durability of the plate.

Various studies have been made so far for the purpose of improving the printing durability. JP-A-5-533
No. 06, JP-A-5-53307 and the like propose a waterless planographic printing plate in which a flexible primer layer containing a natural protein and a urethane elastomer or a polyurethane and a silane coupling agent is provided between a substrate and a photosensitive layer. However, in any case, not only is it impossible to obtain sufficient printing durability for practical use, but it is also necessary to have a sufficient primer layer thickness to cover the physical properties of the photosensitive layer. There is a problem that the silicone rubber layer or the photosensitive layer is peeled off due to the lack, and in a worse case, the primer layer itself is peeled off from the substrate.

A method of thickening the silicone rubber layer has also been tried, but there is a problem in that the developability is lowered and the ink mileage is lowered.

Japanese Unexamined Patent Publication Nos. 1-154158 and 1
JP-A-154159 and the like attempt to cover the decrease in ink mileage by thickening the silicone rubber layer and adjusting the cell depth by embedding an ink receptive substance, but the decrease in developability is still present. There is a problem that it is difficult to handle practically because it exists and a new process such as embedding of an ink receptive substance is added.

In Japanese Patent Application Laid-Open No. 1-1612421, after a plate having an ink inking layer (photosensitive layer) as the uppermost layer is imagewise exposed and developed, an ink repellent layer (silicone rubber layer) is applied and then further developed. A waterless lithographic printing plate having a thick-film silicone rubber layer obtained thereby has been proposed. However, the plate obtained by this method not only has the problem that the ink receptivity of the image area is poor, but it also involves coating the silicone rubber layer after development of the photosensitive layer and developing twice per plate. And there are many work steps, which is not practical.

Studies have been made to improve the physical properties of the silicone rubber layer. Addition of fillers, polydimethylsiloxane having a high molecular weight, and in JP-A-2-32349, a waterless lithographic printing plate having a microporous layer containing a cured product of an ink-repellent substance, JP-A-2-8847. Proposes a waterless lithographic printing plate containing a graft polymer having a branch of polyorganosiloxane in a silicone rubber layer. However, although all of them have been improved in scratch resistance, the improvement in printing durability was insufficient. In addition, the silicone rubber layer has a problem that the repulsion of ink, which the silicone rubber layer originally has, is reduced.

Japanese Unexamined Patent Publication No. 63-213848 discloses a photosensitive layer containing an acrylic acid derivative copolymer. The acrylic acid derivative copolymer is contained in the photosensitive layer in an amount of 50 wt% or more. There is a problem that the image reproducibility and the adhesiveness with the silicone rubber layer are impaired.
If it is t% or less, there is a problem that the printing durability is insufficient.

Further, JP-A-3-20741 discloses a photosensitive layer containing a polymer compound having a carboxylic acid vinyl ester polymerized unit, and JP-A-3-68946 discloses a photosensitive layer containing hydroxyphenylmethacrylamide. Those containing a derivative copolymer are described, and it is said that a plate which can be developed with an aqueous developer and has excellent printing durability can be obtained. However, since these plates have insufficient solvent resistance of the photosensitive layer against plate cleaning solvents such as plate cleaners and UV ink, not only the image areas are destroyed during printing, but also non-image areas are not damaged. There is a problem that printing durability is deteriorated due to the photosensitive layer being attacked by a solvent.

[0013]

The present invention was devised in view of the above-mentioned drawbacks of the prior art. The tensile property of the photosensitive layer is defined by the initial elastic modulus, 10% stress, and elongation at break to make it flexible. By doing so, it is intended to provide a waterless planographic printing plate precursor having a significantly improved printing durability without deteriorating the developability, image reproducibility, printing characteristics, solvent resistance and the like of the plate.

[0014]

The objects of the present invention are as follows: (1) A waterless planographic printing plate precursor obtained by laminating a photosensitive layer containing at least a quinonediazide compound and a binder polymer and an ink repellent layer in this order on a substrate. In the waterless planographic printing plate precursor, the tensile property of the photosensitive layer has a physical property of initial elastic modulus of 5 to 50 kgf / mm @ 2.

(2) The waterless lithographic printing plate precursor as described in (1), wherein the tensile property of the photosensitive layer has a physical property of 10% stress: 0.05 to 3.0 kgf / mm 2.

(3) The waterless planographic printing plate precursor as described in (1), wherein the tensile properties of the photosensitive layer have a physical property of elongation at break: 10% or more.

(4) In a waterless planographic printing plate precursor in which a primer layer, a photosensitive layer containing at least a quinonediazide compound and a binder polymer, and an ink repellent layer are laminated in this order on a substrate, the tensile property of the primer layer is Initial elastic modulus: A waterless planographic printing plate precursor having physical properties of 5 to 50 kgf / mm @ 2.

(5) The waterless planographic printing plate precursor as described in (4), wherein the tensile property of the primer layer has a physical property of 10% stress: 0.05 to 3.0 kgf / mm 2.

(6) The waterless planographic printing plate precursor as described in (4), wherein the tensile property of the primer layer has a physical property of elongation at break: 10% or more.

(7) In a waterless lithographic printing plate precursor in which a primer layer, a photosensitive layer containing at least a quinonediazide compound and a binder polymer, and an ink repellent layer are laminated in this order on a substrate, the primer layer and the photosensitive layer A waterless planographic printing plate precursor characterized in that the tensile properties of the combined layers have the following physical properties: initial elastic modulus: 5 to 50 kgf / mm @ 2.

(8) Water-free according to item (7), characterized in that the tensile properties of the combined layer of the primer layer and the photosensitive layer are 10% stress: 0.05 to 3.0 kgf / mm @ 2. Original planographic printing plate.

(9) The waterless planographic printing plate precursor as described in (7), characterized in that the tensile properties of the combined layer of the primer layer and the photosensitive layer have a breaking elongation of 10% or more.

(10) In a waterless planographic printing plate precursor in which a photosensitive layer containing at least a quinonediazide compound and a binder polymer and an ink repellent layer are laminated in this order on a substrate, the tensile properties of the photosensitive layer after exposure are initially Elastic modulus: A waterless planographic printing plate precursor characterized by having physical properties of 5 to 50 kgf / mm @ 2.

(11) The waterless planographic printing plate precursor as described in (10), wherein the tensile property of the photosensitive layer after exposure has a physical property of 10% stress: 0.05 to 3.0 kgf / mm 2.

(12) The waterless planographic printing plate precursor as described in (10), characterized in that the tensile properties of the photosensitive layer after exposure have physical properties of elongation at break: 10% or more.

(13) In a waterless planographic printing plate precursor in which a primer layer, a photosensitive layer containing at least a quinonediazide compound and a binder polymer, and an ink repellent layer are laminated in this order on a substrate, the primer layer and the photosensitive layer. A waterless lithographic printing plate precursor characterized in that the tensile properties of the combined layers after exposure have physical properties of an initial elastic modulus of 5 to 50 kgf / mm @ 2.

(14) The tensile properties after exposure of the combined layer of the primer layer and the photosensitive layer have a physical property of 10% stress: 0.05 to 3.0 kgf / mm 2 (13) Description Waterless planographic printing plate original.

(15) The waterless lithographic printing plate as described in (13), wherein the tensile properties after exposure of the combined layer of the primer layer and the photosensitive layer have a breaking elongation of 10% or more. Original version.

Is achieved by

The structure of the present invention will be described more specifically below.

A feature of the present invention is that the tensile properties of the photosensitive layer, the primer layer in the case of providing the primer layer, or a layer obtained by combining both layers are (1) Elasticity: 5 to 50 kgf / mm @ 2, preferably (2) 10% stress: 0.05 to 3.0 kgf / mm @ 2 (3) Elongation at break: 10% or more Is.

The initial elastic modulus of these tensile properties is 5 kg.
f / mm2 or more and 50 kgf / mm2 or less, preferably 7
It is important to set the pressure to not less than kgf / mm2 and not more than 45 kgf / mm2, and more preferably not less than 10 kgf / mm2 and not more than 40 kgf / mm2. Initial elastic modulus is 5 kgf / m
When it is less than m2, the photosensitive layer becomes sticky and causes a hickiness during printing.

The 10% stress value is 0.05 kgf /
mm2 or more and 3.0 kgf / mm2 or less are preferable, and 0.1 kgf / mm2 or more and 2.0 kgf / m are more preferable.
It is important to set m2 or less, more preferably 0.1 kgf / mm2 or more and 1.5 kgf / mm2 or less. 1
If the 0% stress value is less than 0.05 kgf / mm @ 2, the photosensitive layer becomes sticky and becomes a hickie during printing. Conversely, 1
When the 0% stress value exceeds 3.0 kgf / mm2,
High printing durability cannot be obtained because breakage occurs at the adhesive interface between the photosensitive layer and the silicone rubber layer due to the repeated stress generated during offset printing.

The breaking elongation is preferably 10% or more, more preferably 15% or more, still more preferably 20.
It is important to make it more than%. When the breaking elongation is less than 10%, the photosensitive layer becomes brittle, and when offset printing is performed, the photosensitive layer is broken and high printing durability cannot be obtained.

The initial elastic modulus exceeds 50 kgf / mm 2,
When the breaking elongation is less than 10%, for example, Japanese Patent Publication No. 61-54
Since the photosensitive layer described in Example 1 of JP-A 222-222 is a hard photosensitive layer having an initial tensile modulus of elasticity of 56 kgf / mm @ 2 and an elongation at break of 5.0%, the photosensitive layer and the silicone rubber layer when offset printing is performed. A stress is repeatedly applied between the two layers, and the photosensitive layer itself is destroyed and the adhesive layer with the silicone rubber layer is subsequently destroyed, and high printing durability cannot be obtained.

The tensile properties can be measured according to JIS K6301.

Regarding the tensile properties before exposure, a photosensitive solution is applied on a glass plate, the solvent is volatilized, and then the composition is heated and cured at 115 ° C. Then, the sheet is peeled from the glass plate to obtain a photosensitive layer sheet having a thickness of about 100 μm. A 5 mm × 40 mm strip-shaped sample was cut out from this sheet, and Tensilon RTM-100 (manufactured by Orientec Co., Ltd.) was used to obtain an initial elastic modulus at a tensile speed of 20 cn / min.
The 10% stress value and the breaking elongation are measured.

When measuring the tensile properties of the primer layer,
A primer solution is used instead of the above photosensitive solution. When the tensile properties of the combined layer of the primer layer and the photosensitive layer are measured, the photosensitive layer is formed on the primer layer by the above method, and the same measurement is performed.

Regarding the tensile properties after exposure, a photosensitive solution is applied on a glass plate, the solvent is volatilized, and then the composition is heated and cured at 115.degree. Then, using a 3 kW ultra-high pressure mercury lamp (Oak Seisakusho), a 10-minute exposure was performed with a UV meter (Oak Seisakusho Light Measure Type UV365) at an illuminance of 12 mW / cm ² . Then, the sheet is peeled from the glass plate to obtain a photosensitive layer sheet having a thickness of about 100 μm. A 5 mm × 40 mm strip-shaped sample is cut out from this sheet, and Tensilon RTM-100 (manufactured by Orientec Co., Ltd.) is used to measure the initial elastic modulus, 10% stress value, and breaking elongation at a tensile speed of 20 cn / min.

When measuring the tensile properties of the primer layer,
A primer solution is used instead of the above photosensitive solution. When the tensile properties of the combined layer of the primer layer and the photosensitive layer are measured, the photosensitive layer is formed on the primer layer by the above method, and the same measurement is performed.

When the tensile properties after exposure are measured from a waterless planographic printing plate precursor, a metal halide lamp (Idlefin 2000 manufactured by Iwasaki Electric Co., Ltd.) is used and a UV meter (light measure type UV-40 manufactured by Oak Manufacturing Co., Ltd.) is used.
2A) for 10 minutes with an illumination intensity of 11 mW / cm ² .
After exposure, if there is a cover film, peel it off,
"Isopar H" / at a room temperature of 32 ° C and a humidity of 80%
Diethylene glycol dimethyl ether / ethyl cellosolve / N-methyldiethanolamine = 87/7/3 /
The treatment liquid consisting of 3 (weight ratio) is applied to the plate surface using a brush. After processing for 1 minute, the processing solution adhering to the plate surface was removed with a rubber squeegee, and then the developing solution (water / butyl carbitol / 2-ethyl acetic acid = 70/30 /
2) Pour (weight ratio), lightly rub the plate surface with a developing pad to remove the silicone rubber layer, and expose the photosensitive layer surface. The support on the back side of the plate which has been subjected to such treatment can be removed by an appropriate method to obtain a sheet having a photosensitive layer or a layer including a primer layer and a photosensitive layer. In the case where the support is a metal plate, one example is a method of scraping off the metal plate with a metal polishing machine, and in the case of a plastic film or sheet, scraping off the plastic support with a plastic polishing machine. In some cases, the photosensitive layer sheet may be removed from the support by using a suitable solvent. In the case of a rubber elastic support or paper, an appropriate solvent is used, or the support is removed by a physical method similar to the above. In this way, an exposed photosensitive layer sheet can be obtained. Using the sheet thus obtained, the initial elastic modulus, elongation at break, and 10% stress value are measured by the methods described above.

The photosensitive layer used in the present invention contains at least a quinonediazide compound and a binder polymer, and a photo-peeling photosensitive layer is mentioned as an example. The photoremovable photosensitive layer means a layer in which the silicone rubber layer thereon is removed by developing, without substantially removing the exposed photosensitive layer. Such a photo-releasing photosensitive layer is modified by cross-linking a quinone diazide compound with a polyfunctional compound to form a cross-linked structure, or by modifying an active group in the quinone diazide compound with a mono-functional compound to make it difficult to develop. It can be obtained by making it soluble or insoluble. Preferably, the quinonediazide compound is crosslinked with a polyfunctional compound.

The quinonediazide compound referred to herein includes quinonediazide compounds used in positive PS plates, Wipon plates, photoresists and the like. Specifically, for example, 1,2-benzoquinonediazide-4-sulfonic acid chloride, 1,2-naphthoquinonediazide-4-sulfonic acid chloride, 1,2-naphthoquinonediazide-
Condensates of 5-sulfonic acid chloride, 1,2-naphthoquinonediazide-6-sulfonic acid chloride and a compound containing a hydroxyl group and / or an amino group are preferably used.

Examples of the hydroxyl group-containing compound include dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dihydroxyanthraquinone, bisphenol A, phenol formaldehyde novolac resin (phenol, p-tert-butylphenol, p-octylphenol, p-nonylphenol, Soluble fusible resin obtained by condensing phenols such as cardanol, cresol, xylenol, catechol and pyrogallol and formaldehydes in the presence of an acidic catalyst), resole resin (for example,
Resin obtained by condensing the above phenols and formaldehyde in the presence of an alkali catalyst), resorcin benzaldehyde condensation resin, pyrogallol acetone resin, p
-Hydroxystyrene copolymer resin, poly-4-vinylphenol, poly-4-oxymethacrylanilide, polyvinyl alcohol, cellulose and its derivatives, chitin, chitosan, polyurethane having a hydroxyl group and the like. Examples of the amino group-containing compound include aniline, p-aminodiphenylamine, p-aminobenzophenone, 4,4′-diaminodiphenylamine, 4,
There are 4'-diaminobenzophenone, poly-4-aminostyrene and the like.

With regard to the quinonediazide compounds including those described here, "Photosensitive polymer" by Nagamatsu and Inui (published by Kodansha, 1977) and "New Photosensitive Resin" by Tsunoda.
(Published by Printing Society of Japan, published in 1981), jointly written by Yamada and Morita, "Photosensitive Resin" edited by The Polymer Society of Japan (Kyoritsu Shuppan, 1988).
(Published annually) and Tsuda, "Surface Science Society of Japan""Molecular Design of VLSI Resist" (Kyoritsu Shuppan, published in 1990).

Among these quinonediazide compounds,
A combination of 1,2-naphthoquinone-2-diazide-5-sulfonic acid chloride and a phenol formaldehyde novolak resin is preferable, and a phenol formaldehyde novolak resin in which 15% to 60% of the hydroxyl groups of the phenol formaldehyde resin are esterified is more preferable. 1,2-naphthoquinone-2-diazide-5-sulfonic acid ester.

Examples of the polyfunctional compound used for introducing the crosslinked structure include polyfunctional isocyanates and polyfunctional epoxy compounds shown below.

Examples of polyfunctional isocyanates include paraphenylene diisocyanate, 2,4- or 2,6-toluylene diisocyanate (TDI), 4,4-diphenylmethane diisocyanate (MDI), tolidine diisocyanate (TODI) and xylylene diisocyanate ( XDI), hydrogenated xylylene diisocyanate, cyclohexane diisocyanate, metaxylylene diisocyanate (MXDI), hexamethylene diisocyanate (HDI or HMDI), lysine diisocyanate (LDI) (also known as 2,6-diisocyanate methyl caproate), hydrogenated MDI (H12MDI) (also known as 4,4′-methylenebis (cyclohexyl isocyanate)), hydrogenated TDI (HTDI) (also known as methylcyclohexane 2,4 (2,2 ) Diisocyanate), hydrogenated XDI (H6 XDI) (also known as 1,3- (isocyanatomethyl) cyclohexane), isophorone diisocyanate (IPDI), diphenyl ether isocyanate,
Trimethylhexamethylene diisocyanate (TMD
I), tetramethylxylylene diisocyanate, polymethylene polyphenyl isocyanate, dimer acid diisocyanate (DDI), triphenylmethane triisocyanate, tris (isocyanatophenyl) thiophosphate, tetramethylxylylene diisocyanate, lysine ester triisocyanate, 1,6 , 11
-Undecane triisocyanate, 1,8-diisocyanate-4-isocyanatomethyl octane, 1,3
Examples thereof include 6-hexamethylene triisocyanate, bicycloheptane triisocyanate and the like, polyhydric alcohol adducts of polyisocyanates, and polymers of polyisocyanates.

Examples of polyfunctional epoxy compounds include polyethylene glycol diglycidyl ethers, polypropylene glycol diglycidyl ethers, bisphenol A diglycidyl ether, trimethylolpropane triglycidyl ether and the like.

Among these, preferred are polyfunctional isocyanate compounds.

The amount of these polyfunctional compounds used is preferably 1 to 150 parts by weight, more preferably 5 to 100 parts by weight, and even more preferably 10 to 80 parts by weight, based on 100 parts by weight of the quinonediazide compound.

It is necessary to carry out heat curing of these at a temperature at which the photosensitivity of the quinonediazide compound is not lost, usually at 150 ° C. or lower. For this reason, it is preferable to use a catalyst in combination.

As a method of reacting a monofunctional compound with a quinonediazide compound to modify it to make it insoluble or insoluble in a developing solution, similarly, the active group of the quinonediazide compound is esterified, amidated or urethane-modified. There are things like that. The compound reacted with the active group of the quinonediazide compound may be a low molecular weight compound or a relatively high molecular weight compound, or a monomer may be graft-polymerized to the photosensitive compound.

As the binder polymer having the function of retaining the shape in the present invention, any binder can be used as long as it is soluble in an organic solvent and has a film-forming ability, but its glass transition temperature (Tg) is preferable. Polymers and copolymers at 0 ° C. or lower can be mentioned.

Glass transition temperature Tg (glass transition t
Emperature) refers to the transition point (temperature) at which the physical properties of the amorphous polymer material change from the glass state to the rubber state (or vice versa). In a relatively narrow temperature range around the transition point, not only the elastic modulus but also various properties such as expansion coefficient, heat content, refractive index, diffusion coefficient, and dielectric constant change greatly. Therefore, the glass transition temperature is measured by measuring the volume (specific volume) -temperature curve, measuring the heat content by thermal analysis (DSC, DTA, etc.), measuring the properties of the substance as a whole such as refractive index and stiffness. Some measure the amount that reflects molecular motion such as (dynamic viscoelasticity), dielectric loss tangent, and NMR spectrum. It is customary to use a dilatometer to measure the volume of the sample while raising the temperature and determine it as the point where the slope of the volume (specific volume) -temperature curve changes abruptly.

Typical polymers that can be used as the binder polymer will be specifically described below, but the present invention is not limited thereto.

(1) Vinyl Polymers Polymers and copolymers obtained from the following monomers and their derivatives.

For example, ethylene, propylene, 1-butene, styrene, butadiene, isoprene, vinyl chloride,
Vinyl acetate, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, N-hexyl methacrylate, lauryl methacrylate, acrylic acid,
Methacrylic acid, maleic acid, itaconic acid, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, polyethylene glycol mono (meth) acrylate, polypropylene Glycol mono (meth) acrylate, phenoxyethyl (meth) acrylate, 2- (meth) acryloxyethyl hydrogen phthalate, 2- (meth) acryloxyethyl hydrogen succinate, acrylamide, N-methylol acrylamide, diacetone acrylamide, glycidyl methacrylate, Acrylonitrile, styrene, vinyltoluene, isobutene, 3-methyl-1-butene, butyl vinyl ether, N-vinylcarbazole, methyl vinyl ketone, nitroethyl Emissions, alpha-cyano acrylic acid methyl,
Vinylidene cyanide, polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth)
Acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyl) Oxypropyl)
After adding ethylene oxide or propylene oxide to a polyfunctional alcohol such as ether, glycerin, trimethylolethane, or trimethylolpropane (meth)
An acrylated polymer and a polymer or copolymer obtained by polymerizing or copolymerizing these derivatives can be used as the binder polymer.

Specific examples of the vinyl-based polymer having a glass transition temperature of 0 ° C. or lower include, but are not limited to, the following polymers.

(A) Polyolefins For example, poly (1-butene), poly (5-cyclohexyl-1-pentene), poly (1-decene), poly (1,1)
-Dichloroethylene), poly (1,1-dimethylbutane), poly (1,1-dimethylpropane), poly (1-
Dodecene), polyethylene, poly (1-heptene), poly (1-hexene), polymethylene, poly (6-methyl-1-heptene), poly (5-methyl-1-hexene), poly (2-methylpropene) , Poly (1-nonene), poly (1-octene), poly (1-pentene),
Poly (5-phenyl-1-pentene), polypropylene, polyisobutylene, poly (1-butene) and the like.

Further, poly (vinyl butyl ether), poly (vinyl ethyl ether), poly (vinyl isobutyl ether), poly (vinyl methyl ether) and the like.

(B) Polystyrenes Examples of polystyrene derivatives having a glass transition temperature of 0 ° C. or lower include poly (4-[(2-butoxyethoxy) methyl] styrene), poly (4-decylstyrene), and poly (4-dodecyl). Styrene), poly [4- (2-ethoxyethoxymethyl) styrene], poly [4- (1-ethylhexoxymethyl) styrene], poly [4- (hexoxymethyl) styrene], poly (4-hexylstyrene), Examples thereof include poly (4-nonylstyrene), poly [4- (octoxymethyl) styrene], poly (4-octylstyrene), and poly (4-tetradecylstyrene).

(C) Acrylic ester polymer and methacrylic acid ester polymer Examples of polyacrylates having a glass transition temperature of 0 ° C. or lower include, for example, poly (butyl acrylate), poly (sec-butyl acrylate), and poly (tert-butyl acrylate). , Poly [2- (2-cyanoethylthio) ethyl acrylate], poly [3- (2-cyanoethylthio) propyl acrylate], poly [2- (cyanomethylthio)]
Ethyl acrylate], poly [6- (cyanomethylthio) hexyl acrylate], poly [2- (3-cyanopropylthio) ethyl acrylate], poly (2-ethoxyethyl acrylate), poly (3-ethoxypropyl acrylate), poly (Ethyl acrylate), poly (2-ethylbutyl acrylate), poly (2-ethylhexyl acrylate), poly (5-ethyl-2-nonyl acrylate), poly (2-ethylthioethyl acrylate), poly (3-ethylthio) Propyl acrylate), poly (heptyl acrylate), poly (2-heptyl acrylate), poly (hexyl acrylate),
Poly (isobutyl acrylate), poly (isopropyl acrylate), poly (2-methoxyethyl acrylate), poly (3-methoxypropyl acrylate), poly (2-methylbutyl acrylate), poly (3-methylbutyl acrylate), poly ( 2-methyl-7-ethyl-4-undecyl acrylate), poly (2-methylpentyl acrylate), poly (4-methyl-2-pentyl acrylate), poly (4-methylthiobutyl acrylate), poly (2-methylthio). Ethyl acrylate), poly (3-methylthiopropyl acrylate),
Poly (nonyl acrylate), poly (octyl acrylate), poly (2-octyl acrylate), poly (3
-Pentyl acrylate), poly (propyl acrylate), poly (hydroxyethyl acrylate), poly (hydroxypropyl acrylate) and the like can be mentioned as typical examples.

Examples of polymethacrylates having a glass transition temperature of 0 ° C. or lower include poly (decyl methacrylate), poly (dodecyl methacrylate), poly (2-ethylhexyl methacrylate), poly (octadecyl methacrylate), poly (octyl methacrylate), poly (octyl methacrylate), and the like. (Tetradecyl methacrylate), poly (n-hexyl methacrylate), poly (lauryl methacrylate)
Etc.

(2) Unvulcanized rubber A natural rubber (NR) or a homopolymer or a copolymer selected from butadiene, isoprene, styrene, acrylonitrile, acrylic acid ester and methacrylic acid ester, such as polybutadiene (BR). ), Styrene-butadiene copolymer (SBR), carboxy-modified styrene-butadiene copolymer, polyisoprene (NR), polyisobutylene, polychloroprene (CR), polyneoprene, acrylic ester-butadiene copolymer, methacryl Acid ester-butadiene copolymer, acrylic acid ester-acrylonitrile copolymer (ANM), isobutylene-isoprene copolymer (IIR), acrylonitrile-butadiene copolymer (NBR), carboxy-modified acrylonitrile-butadiene copolymer, A Acrylonitrile-chloroprene copolymer, acrylonitrile-isoprene copolymer, ethylene-propylene copolymer (EP
M, EPDM), vinyl pyridine-styrene-butadiene copolymer, styrene-isoprene copolymer and the like. These unvulcanized rubbers generally have a glass transition temperature of 0 ° C. or lower.

In addition to these, specific examples of rubbers having a glass transition temperature of 0 ° C. or lower are, for example, poly (1,3-butadiene), poly (2-chloro-1,3-butadiene), poly (2-). Decyl-1,3-butadiene), poly (2,3
-Dimethyl-1,3-butadiene), poly (2-ethyl-1,3-butadiene), poly (2-heptyl-1,3)
-Butadiene), poly (2-isopropyl-1,3-butadiene), poly (2-methyl-1,3-butadiene), chlorosulfonated polyethylene and the like, but are not limited thereto.

Further, modified products of these rubbers, for example, rubbers which are usually modified by epoxidation, chlorination, carboxylation and the like, and blends with other polymers can also be used as the binder polymer.

(3) Polyoxides (Polyethers) Trioxane, ethylene oxide, propylene oxide, 2,3-epoxybutane, 3,4-epoxybutene, 2,3-epoxypentane, 1,2-epoxyhexane, epoxycyclohexane. , Epoxycycloheptane, epoxycyclooctane, styrene oxide, 2-
Phenyl-1,2-epoxypropane, tetramethylethylene oxide, epichlorohydrin, epibromohydrin, allyl glycidyl ether, phenyl glycidyl ether, n-butyl glycidyl ether, 1,4-dichloro-2,3-epoxybutane, 2, Polymers and copolymers can also be used as the binder polymer by ring-opening polymerization of 3-epoxypropionaldehyde, 2,3-epoxy-2-methylpropionaldehyde, 2,3-epoxydiethyl acetal and the like.

Specific examples of polyoxides having a glass transition temperature of 0 ° C. or lower include, for example, polyacetaldehyde, poly (butadiene oxide), poly (1-butene oxide), poly (dodecene oxide), poly (ethylene oxide), poly ( Isobutene oxide), polyformaldehyde, poly (propylene oxide), poly (tetramethylene oxide), poly (trimethylene oxide) and the like.

(4) Polyesters Polyesters obtained by polycondensation of polyhydric alcohols and polycarboxylic acids as shown below, polyesters obtained by polymerization of polyhydric alcohols and polycarboxylic acid anhydrides, ring opening of lactones Polyester obtained by polymerization and the like, polyester obtained from a mixture of these polyhydric alcohols, polyvalent carboxylic acids, polyvalent carboxylic anhydrides, and lactones can also be used as the binder polymer.

As the polyhydric alcohol, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, Diethylene glycol, dipropylene glycol, neopentyl glycol, triethylene glycol, p-xylylene glycol, hydrogenated bisphenol A, bisphenol dihydroxypropyl ether, glycerin, trimethylolethane, trimethylolpropane, trishydroxymethylaminomethane, pentaerythritol, Dipentaerythritol, sorbitol, etc.

Examples of the polycarboxylic acid and polycarboxylic anhydride include phthalic anhydride, isophthalic acid, terephthalic acid, succinic anhydride, adipic acid, azelaic acid, sebacic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, Tetrabromophthalic anhydride, tetrachlorophthalic anhydride, hettic anhydride, hymic acid anhydride, maleic anhydride, fumaric acid, itaconic acid, trimellitic anhydride,
Methyl cyclohexene tricarboxylic acid anhydride, pyromellitic dianhydride, etc.

Examples of the lactone include β-propiolactone, γ-butyrolactone, δ-valerolactone and ε-caprolactone.

Specific examples of the polyester having a glass transition temperature of 0 ° C. or lower include, for example, poly [1,4- (2-butene)].
Sebacate], poly [1,4- (2-butyne) sebacate], poly (decamethylene adipate), poly (ethylene adipate), poly (oxydiethylene adipate), poly (oxydiethylene azelaate), poly (Oxydiethylene dodecane diate), poly (oxydiethylene glutarate), poly (oxydiethylene heptyl malonate), poly (oxydiethylene malonate), poly (oxydiethylene methyl malonate), poly (oxydiethylene nonyl malonate) , Poly (oxydiethylene octadecane diate), poly (oxydiethylene oxalate), poly (oxydiethylene pentyl malonate), poly (oxydiethylene pimelate), poly (oxydiethylene propyl malonate),
Poly (oxydiethylene sebacate), poly (oxydiethylene suberate), poly (oxydiethylene succinate), poly (pentamethylene adipate), poly (tetramethylene adipate), poly (tetramethylene sebacate), poly (Trimethylene adipate) and the like, but not limited to these.

(5) Polyurethanes Polyurethanes obtained from the following polyisocyanates and polyhydric alcohols can also be used as the binder polymer. As the polyhydric alcohol, the polyhydric alcohols described in the above section of polyester and the following polyhydric alcohols, and both ends obtained by polycondensation of these polyhydric alcohol and the polyvalent carboxylic acid described in the section of polyester are hydroxyl groups Such condensed polyester polyols, polymerized polyester polyols obtained from the above lactones, polycarbonate diols, polyether polyols obtained by ring-opening polymerization of propylene oxide or tetrahydrofuran, or modification of epoxy resin, or acrylic (or methacrylic) monocarboxylic acid having a hydroxyl group. Acrylic polyols, polybutadiene polyols, and the like, which are copolymers of monomers and acrylic (or methacrylic) acid esters, can be used.

The isocyanates include paraphenylene diisocyanate, 2,4- or 2,6-toluylene diisocyanate (TDI), 4,4-diphenylmethane diisocyanate (MDI), tolidine diisocyanate (TODI), xylylene diisocyanate (X
DI), hydrogenated xylylene diisocyanate, cyclohexane diisocyanate, metaxylylene diisocyanate (MXDI), hexamethylene diisocyanate (HDI or HMDI), lysine diisocyanate (LDI) (also known as 2,6-diisocyanate methyl caproate), hydrogenated MDI (H12MDI) (Alias 4,
4'-methylenebis (cyclohexyl isocyanate)), hydrogenated TDI (HTDI) (also known as methylcyclohexane 2,4 (2,6) diisocyanate), hydrogenated XDI (H6 XDI) (also known as 1,3- (isocyanatomethyl) cyclohexane) ), Isophorone diisocyanate (IPDI), diphenyl ether isocyanate,
Trimethylhexamethylene diisocyanate (TMD
I), tetramethylxylylene diisocyanate, polymethylene polyphenyl isocyanate, dimer acid diisocyanate (DDI), triphenylmethane triisocyanate, tris (isocyanatophenyl) thiophosphate, tetramethylxylylene diisocyanate, lysine ester triisocyanate, 1,6 , 11
-Undecane triisocyanate, 1,8-diisocyanate-4-isocyanatomethyl octane, 1,3
Examples thereof include 6-hexamethylene triisocyanate, bicycloheptane triisocyanate and the like, polyhydric alcohol adducts of polyisocyanates, and polymers of polyisocyanates.

Typical polyhydric alcohols other than those mentioned in the section of polyester are polypropylene glycol, polyethylene glycol, polytetramethylene glycol, ethylene oxide-propylene oxide copolymer, tetrahydrofuran-ethylene oxide copolymer. , Tetrahydrofuran-propylene oxide copolymer and the like, and as the polyester diol, polyethylene adipate, polypropylene adipate,
Polyhexamethylene adipate, polyneopentyl adipate, polyhexamethylene neopentyl adipate,
Examples thereof include polyethylene hexamethylene adipate and the like, and poly-ε-caprolactone diol, polyhexamethylene carbonate diol, polytetramethylene adipate, sorbitol, methyl glucogit, sucrose and the like.

Also, various phosphorus-containing polyols, halogen-containing polyols, etc. can be used as the polyol.

Furthermore, branched polyurethane resins and polyurethane resins having various functional groups such as hydroxyl groups can also be used as the binder polymer.

In addition to these, poly (tetramethylene hexamethylene-urethane), poly (1,4- (2-butene))
Hexamethylene-urethane), poly (1,4- (2-butyne) hexamethylene-urethane) and the like,
It is not limited to these.

These polyurethanes generally have a glass transition temperature of 0 ° C. or lower.

(6) Polyamides Conventionally proposed polyamides can also be used as the binder polymer.

The basic composition is a copolymer of the following monomers. ε-caprolactam, ω-laurolactam, ω-aminoundecanoic acid, hexamethylenediamine, 4,4′-bis-aminocyclohexylmethane, 2,4,4-trimethylhexamethylenediamine,
Isophorone diamine, diglycols, isophthalic acid,
Adipic acid, sebacic acid, dodecanedioic acid, etc.

More specifically, polyamides are generally classified into water-soluble polyamides and alcohol-soluble polyamides. Examples of the water-soluble polyamide include those disclosed in
Polyamide containing sulfonic acid group or sulfonate group obtained by copolymerizing sodium 3,5-dicarboxybenzene sulfonate as shown in JP-A-48-72250, disclosed in JP-A-49-43465. A polyamide having an ether bond, which is obtained by copolymerizing any one of a dicarboxylic acid having an ether bond in the molecule, a diamine, or a cyclic amide, as described in JP-A-50-7605. Basic nitrogen-containing polyamides obtained by copolymerizing N, N′-di (γ-aminopropyl) piperazine, etc., as shown, and polyamides obtained by quaternizing these polyamides with acrylic acid, etc. A copolymerized polyamide containing a polyether segment having a molecular weight of 150 to 1500, which is proposed in JP-A-55-74537, and α (N, N'-dialkylamino)-.epsilon.-caprolactam ring-opening polymerization or α of
Examples thereof include polyamides obtained by ring-opening copolymerization of-(N, N'-dialkylamino) -ε-caprolactam and ε-caprolactam.

Examples of alcohol-soluble polyamides include linear polyamides synthesized by a known method from dibasic acid fatty acids and diamines, ω-amino acids, lactams or derivatives thereof, and not only homopolymers but also copolymers, block polymers and the like. Can also be used. Typical examples are nylon 3, 4, 5, 6, 8, 11, 1
2, 13, 66, 610, 6/10, 13/13, polyamide from metaxylylenediamine and adipic acid, trimethylhexamethylenediamine or polyamide from isophoronediamine and adipic acid, ε-caprolactam / adipic acid / hexamethylene Diamine / 4,4 '
-Diaminodicyclohexylmethane copolymerized polyamide,
ε-caprolactam / adipic acid / hexamethylenediamine / 2,4,4′-trimethylhexamethylenediamine copolymerized polyamide, ε-caprolactam / adipic acid / hexamethylenediamine / isophoronediamine copolymerized polyamide, or polyamide containing these components ,
Those N-methylol, N-alkoxymethyl derivative, etc. can also be used.

The above polyamides can be used alone or in combination as a binder polymer.

As the polyamide having Tg of 0 ° C. or lower, a copolyamide containing a polyether segment having a molecular weight of 150 to 1500, more specifically, having a terminal amino group and a polyether segment having a molecular weight of 150 to 1 is used.
30 to 70% by weight of a constitutional unit composed of polyoxyethylene of 500 and an aliphatic dicarboxylic acid or diamine
Examples thereof include, but are not limited to, the copolymerized polyamide that is contained.

These polymers which can be used as the binder polymer may be used alone or as a mixture of several kinds of polymers.

Among these binder polymers, polyurethane, polyester, vinyl polymer and unvulcanized rubber are preferable.

The binder polymer is preferably used in an amount of 15 to 80 wt% with respect to the components of the photosensitive layer.
A more preferred amount used is 15 to 65 wt%, and a most preferred amount is 20 to 55 wt%.

Further, 15 to 80 wt% of the binder polymer with respect to the photosensitive layer component and 1,2-naphthoquinone-2-diazide-5, which is a phenol formaldehyde novolac resin having an esterification rate of 15 to 60% as a quinonediazide compound.
The combination of sulphonic acid esters results in the most preferred composition.

When the quinonediazide sulfonic acid esterification rate of the hydroxyl groups of the phenol-formaldehyde resin is less than 15%, the number of photosensitive groups is small, so that the image reproducibility,
There arises a problem that the developability is deteriorated. On the other hand, when the esterification rate is higher than 60%, it means that the residual hydroxyl group, that is, the number of cross-linking points is decreased, and therefore the solvent resistance of the photosensitive layer and the SK adhesive strength (adhesive strength between the photosensitive layer and the silicone rubber layer) are problematic. cause.

When the content of the binder polymer is less than 15% by weight, it is difficult to develop satisfactory physical properties of the photosensitive layer. On the other hand, when the content of the binder polymer is more than 80% by weight, it means that the amount of the quinonediazide compound is reduced. This causes problems in reproducibility, developability, SK adhesive strength and the like.

In addition to the above components, it is optional to add additives such as acids, dyes, pigments, photochromic agents and catalysts to the photosensitive layer composition, if necessary.

The thickness of the light-peeling photosensitive layer is 0.1 to 100 μm.
m is preferable, and more preferably about 0.5 to 10 μm. If it is too thin, pinholes are likely to occur in the photosensitive layer, while if it is too thick, it is economically disadvantageous, so the above range is preferred.

Examples of the ink repellent layer used in the present invention include, but are not limited to, those using silicone rubber and those using fluororesin.

When silicone rubber is used as the ink repellent layer, the silicone rubber layer may be of the following general formula (I)
The main component is a linear organic polysiloxane having a molecular weight of several thousand to several hundred thousand and having such a repeating unit.

Embedded image Here, n is an integer of 2 or more, and R is an alkyl group having 1 to 10 carbon atoms, an alkenyl group, a phenyl group, or a cyanoalkyl group. 40% or less of the total R is vinyl, phenyl, vinyl halide, phenyl halide, R
It is preferable that 60% or more of them are methyl groups. Such a linear organic polysiloxane can be made into a sparsely crosslinked silicone rubber by adding an organic peroxide and subjecting it to heat treatment.

A crosslinking agent as shown below is added to the linear organic polysiloxane. Rn SiX4-n (in the formula, n is an integer of 1 to 3, R represents an alkyl group, an aryl group, an alkenyl group or a monovalent group in which these are combined, and these are a halogen atom, an amine group, a hydroxy group Group, alkoxy group, aryloxy group, (meth)
You may have functional groups, such as an acryloxy group and a thiol group. X is --OH, --OR2, --OAc, --ON--C
(R2) R3) represents a substituent such as -Cl, -Br and -I. Here, R2 and R3 have the same meanings as R described above, and R2 and R3 may be the same or different. Ac represents an acetyl group. The crosslinking agent may be a polyfunctional silane compound used in the so-called room temperature (low temperature) curable silicone rubber as described above. For example, acetoxysilane having a trimethoxysilyl group, amino group, glycidyl group, methacryl group, allyl group, vinyl group and the like, ketoxime silane, alkoxysilane, aminosilane, amidosilane and the like.

These are usually combined with linear organic polysiloxanes having terminal hydroxyl groups to form deacetic acid type, deoxime type, dealcohol type, deamine type and deamide type silicone rubbers.

Silicone rubbers which are subjected to such condensation type crosslinking include metal carboxylates of tin, zinc, lead, calcium, manganese, etc., such as dibutyltin laurate, tin (II) octoate, naphthenate, or the like. A catalyst such as chloroplatinic acid may be added.

An addition type silicone rubber layer which is crosslinked by an addition reaction between a SiH group and a -CH = CH- group is also useful. The addition type silicone rubber layer used here is composed of polyvalent hydrogenorganopolysiloxane and 2 per molecule.
Obtained by reaction with a polysiloxane compound having one or more -CH = CH- bonds, preferably the following components: (1) Alkenyl group (preferably vinyl group) directly bonded to silicon atom in one molecule. 100 parts by weight of organopolysiloxane having at least two (2) Organopolysiloxane having at least two SiH bonds in one molecule 0.1 to 1000 parts by weight (3) Addition catalyst 0.00001 to 10 parts by weight Is obtained by crosslinking and hardening. Ingredient (1)
The alkenyl group may be at either the terminal or the middle of the molecular chain. The organic group other than the alkenyl group is a substituted or unsubstituted alkyl group or aryl group. Ingredient (1)
May contain a small amount of hydroxyl groups. The component (2) reacts with the component (1) to form a silicone rubber layer, and plays a role of imparting adhesiveness to the photosensitive layer. The hydroxyl group of the component (2) may be at the terminal of the molecular chain or at the middle thereof. The organic group other than hydrogen is selected from the same groups as the component (1). From the viewpoint of improving the ink resilience, it is preferable that the organic groups of the components (1) and (2) are methyl groups in a total number of 60% or more. The molecular structures of the components (1) and (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, and further the component (1) ) Has a molecular weight of 1,
It is preferably more than 000.

Examples of the component (1) include α, ω-divinylpolydimethylsiloxane and a (methylsiloxane) (dimethylsiloxane) copolymer having methyl groups at both ends, and the component (2) includes hydroxyl groups at both ends. Examples thereof include polydimethylsiloxane, α, ω-dimethylpolymethylhydrogensiloxane, (methylpolymethylhydrogensiloxane) (dimethylsiloxane) copolymer having methyl groups at both terminals, and cyclic polymethylhydrogensiloxane.

The addition catalyst of the component (3) is arbitrarily selected from known ones, but platinum compounds are particularly desirable,
Platinum simple substance, platinum chloride, olefin coordination platinum, etc. are illustrated. For the purpose of controlling the curing rate of these compositions, vinyl group-containing organopolysiloxanes such as tetracyclo (methylvinyl) siloxane, carbon-carbon triple bond alcohols, acetone, methylethylketone, methanol,
It is also possible to add a crosslinking inhibitor such as ethanol or propylene glycol monomethyl ether.

In addition to these compositions, a known adhesion-imparting agent such as alkenyltrialkoxysilane may be added, a hydroxyl group-containing organopolysiloxane which is a composition of a condensation type silicone rubber layer, and a terminal is a trimethylsilyl group. Silicone oil made of dimethylpolysiloxane, dimethylpolysiloxane having a trimethylsilyl group at the end, 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.

The tensile properties of such a silicone rubber layer are such that the initial elastic modulus is 0.008 kgf / mm 2 or more and 0.1.
It is preferably not more than 09 kgf / mm @ 2, more preferably not more than 0.
012 kgf / mm2 or more and 0.07 kgf / mm2 or less, and 50% stress value is 0.005 kgf / mm2 or more and 0.
It is preferably 04 kgf / mm 2 or less, more preferably 0.
It is important to set it to 007 kgf / mm2 or more and 0.025 kgf / mm2 or less.

The above initial elastic modulus is 0.008 kgf / mm
If it is less than 2 and the 50% stress value is less than 0.005 kgf / mm @ 2, printing durability becomes poor. On the other hand, the initial elastic modulus is 0.09
When it exceeds kgf / mm2, 50% stress value is 0.04k
When it exceeds gf / mm2, for example, Japanese Patent Publication No. 56-23
The initial tensile modulus of elasticity of the silicone rubber layer described in Example 1 of JP-A No. 150 is 0.15 kgf / mm @ 2, and the 50% stress value is 0.06 kgf / mm @ 2. Since it is hard as a silicone rubber layer, it is ink repellent and resistant. Scratchability deteriorates.

Further, the breaking elongation of the tensile properties of the silicone rubber layer is preferably 100% or more, more preferably 15%.
It is important to set it to 0% or more and less than 1200%. When the elongation at break is 100% or less, printing durability becomes poor.

The tensile properties of silicone rubber are JIS K
6301. For example,
After applying silicone rubber liquid to the Teflon plate and drying it,
The sheet was peeled off from the Teflon plate, and a test piece was prepared from the obtained sheet having a thickness of about 300 μm with a No. 4 dumbbell.
The initial elastic modulus, 50% stress value, and breaking elongation may be measured according to SK6301.

The thickness of the silicone rubber layer is about 0.5-10.
0 μm, preferably about 0.5-10 μm,
If it is too thin, problems may occur in terms of printing durability and ink repulsion. On the other hand, if it is too thick, it is economically disadvantageous and it becomes difficult to remove the silicone rubber layer during development, resulting in image reproducibility. Bring about a decline.

The substrate used in the present invention may be any of those used in ordinary waterless planographic printing plates or those proposed. That is, it is sufficient that it can be set in an ordinary planographic printing machine and can withstand the load applied during printing.

For example, a metal plate made of aluminum, copper, zinc, steel or the like, or a metal plate plated or vapor-deposited with chromium, zinc, copper, nickel, aluminum, iron or the like,
A plastic film or sheet such as polyethylene terephthalate, polystyrene, polypropylene, etc., a substrate having rubber elasticity such as chloroprene rubber, NBR, or a substrate having such rubber elasticity, or a metal foil such as paper, resin-coated paper, or aluminum. And the like. It is also possible to coat these substrates with other substances for the purpose of preventing halation and for other purposes. Of these, the aluminum plate is preferable.

In the waterless planographic printing plate of the present invention, the adhesion between the substrate and the photosensitive layer and between the photosensitive layer and the silicone rubber layer is very important for basic plate performance such as image reproducibility and printing durability. If necessary, it is possible to provide an adhesive layer between the layers or to add an adhesiveness improving component to each layer. For adhesion between the photosensitive layer and the silicone rubber layer,
It is effective to provide a known silicone primer or silane coupling agent between the layers, or add a silicone primer or silane coupling agent to the silicone rubber layer or the photosensitive layer.

The treatment of the substrate itself for the purpose of adhering the substrate and the photosensitive layer is not particularly limited, and various surface roughening treatments are included.

Before applying the photosensitive layer to the substrate, a primer layer may be provided on the substrate in order to obtain sufficient adhesion between the photosensitive layer and the substrate.

As the resin constituting the primer layer, polyurethane resin, epoxy resin, urea resin, phenol resin, benzoguanamine resin, polyester resin, polyamide resin, vinyl chloride-vinyl acetate copolymer, acrylate copolymer, acrylic resin Resin, vinyl chloride resin, phenoxy resin, polyvinyl butyral resin, ethylene-
Vinyl acetate copolymers, diene rubbers such as polyacrylonitrile-butadiene copolymers, polyvinyl acetate-polycarbonate resins, cellulose and its derivatives, chitin, chitosan, milk casein, gelatin, soy protein, albumin and the like. However, it is not limited thereto. These resins may be used alone or in combination of two or more, and may be used together with other crosslinking agents as described in the photosensitive layer. Among these, it is preferable to use a polyurethane resin, an epoxy resin, a urea resin or the like alone or in combination with another resin.

As the anchor agent constituting the primer layer, for example, a silane coupling agent can be used, and organic titanate or the like is also effective.

In order to prevent halation from the substrate and to improve the plate inspection property, titanium oxide, calcium carbonate,
It is also possible to add a white pigment or a yellow pigment such as zinc oxide.

Further, it is optional to add a surfactant or the like for the purpose of improving the coatability. The composition for forming the above-mentioned primer layer is prepared as a composition solution by dissolving it in a suitable organic solvent such as DMF, methyl ethyl ketone, methyl isobutyl ketone, or dioxane. A primer layer is formed by uniformly applying such a composition solution on a substrate and heating at a required temperature for a required time.

The thickness of the primer layer is selected to be 0.2 to 50 μm, more preferably 0.5 to 20 μm. If it is too thin, the effect of blocking morphological defects and adverse chemical effects on the substrate surface is poor, while if it is too thick, it is economically disadvantageous, so the above range is preferred.

In the waterless lithographic printing plate precursor constructed as described above, in order to protect the surface silicone rubber layer and to improve the vacuum adhesion of the negative film during the exposure step, the silicone rubber layer It is also possible to form a protective layer by laminating a thin protective film having a plain or uneven surface on the surface or applying or transferring a thin plastic sheet material. The protective film and protective layer are useful in the exposure step, but are removed by peeling or dissolution in the developing step and unnecessary in the printing step.

Useful protective films have a UV-transmissive property and a thickness of 100 μm or less, preferably 10 μm or less. Typical examples thereof include polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate and cellophane. I can give you.
The surface of these protective films may be subjected to unevenness processing in order to improve the adhesion with the film. Further, instead of the protective film, a protective layer may be formed by a method such as coating.

The waterless planographic printing plate precursor used in the present invention is produced, for example, as follows. First, a composition that should be used to form a photosensitive layer on a substrate that has been subjected to various surface roughening treatments as necessary, using a normal coater such as a reverse roll coater, an air knife coater, a Mayer bar coater, or a spin coater such as a hoela. The product solution is applied, dried and, if necessary, thermally cured. Incidentally, if necessary, after providing a primer layer between the substrate and the photosensitive layer in the same manner as described above, after applying an adhesive layer on the photosensitive layer in the same manner as necessary, after drying, The silicone rubber solution is applied on the photosensitive layer or the adhesive layer in the same manner, and usually 60 to 130 ° C.
Heat treatment is carried out at a temperature of several minutes for several minutes to fully cure the silicone rubber layer. If necessary, a protective layer is further applied or the protective film is covered on the silicone rubber layer with a laminator or the like.

The waterless planographic printing plate precursor thus produced was, for example, directly or peeled in the case of a light-transmitting protective film, and peeled and vacuum-bonded in the case of a film having a poor light-transmitting property. It is exposed to actinic radiation through a negative film. The light source used in this exposure process is
It emits a large amount of ultraviolet rays, and mercury lamps, carbon arc lamps, xenon lamps, metal halide lamps, tungsten lamps, fluorescent lamps, etc. can be used.

When the protective film is then peeled off, the plate surface is rubbed with a developing pad containing a developing solution to remove only the silicone rubber layer in the exposed area, exposing the surface of the photosensitive layer to become an ink receiving area, and to remove water. None A lithographic printing plate is obtained.

As the developing solution used in the present invention, those usually proposed for waterless planographic printing plates can be used. For example, water, water with the following polar solvent added, aliphatic hydrocarbons (hexane, heptane,
"Isopar" E, G, H (manufactured by Esso Kagaku Co., Ltd.) or gasoline, kerosene, etc., aromatic hydrocarbons (toluene, xylene, etc.) or halogenated hydrocarbons (tricrene, etc.) with the polar solvent below or A polar solvent and water added, or a polar solvent alone is preferable.

Alcohols (methanol, ethanol,
Propanol, benzyl alcohol, ethylene glycol monophenyl ether, 2-methoxyethanol, carbitol monoethyl ether, carbitol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether. , Polyethylene glycol monomethyl ether, propylene glycol, polypropylene glycol, triethylene glycol, tetraethylene glycol, etc.) ethers (methyl cellosolve,
Ethyl cellosolve, butyl cellosolve, methyl carbitol, ethyl carbitol, butyl carbitol, dioxane, etc.) Ketones (acetone, methyl ethyl ketone, 4-methyl-1,3-dioxolan-2-one, etc.) Esters (methyl acetate, ethyl acetate , Methyl lactate, ethyl lactate, butyl lactate, cellosolve acetate, methyl cellosolve acetate, carbitol acetate, propylene glycol monomethyl ether acetate, dimethyl phthalate, diethyl phthalate, etc.) Others (triethyl phosphate, etc.)

It is also possible to use a developer containing various surfactants such as anionic surfactants, nonionic surfactants, cationic surfactants and zwitterionic surfactants, and alkaline agents. Examples of the alkaline agent include inorganic alkaline agents such as sodium carbonate, sodium silicate, sodium hydroxide, potassium hydroxide, and sodium borate, or mono-, di-, or triethanolamine, mono-, di-, or trimethylamine, mono-, di- Or an organic amine compound such as triethylamine, mono- or diisopropylamine, n-butylamine, mono-, di- or triisopropanolamine, ethyleneimine, and ethylenediimine.

It is also possible to add a dye such as crystal violet or astrazone red to the developer to dye the image area at the same time as the development. Alternatively, the plate after development can be dyed as a post-treatment by immersing it in a dyeing solution.

The developing method may be manual development or development by a known developing device, but it is preferable to use a developing device in which a pretreatment section, a development section, and a posttreatment section are provided in this order.

[0130]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

The tensile property test method is as follows.

[Photosensitive Layer, Primer Layer, Layer Composed of Photosensitive Layer and Primer Layer] Tensile properties before exposure Measured according to JIS K6301.

A primer solution or a photosensitive solution was applied on a glass plate, the solvent was volatilized, and then the composition was heated and cured at 115 ° C. After this, peel off the sheet from the glass plate to obtain about 10
A 0 micron thick sheet was obtained. 5m from this sheet
A m × 40 mm strip-shaped sample was cut out, and using Tennsilon RTM-100 (manufactured by Orientec Co., Ltd.), the initial elastic modulus was 10% stress at a tensile speed of 20 cm / min.
The breaking elongation was measured. When examining the tensile properties of the combined layer of the primer layer and the photosensitive layer, a photosensitive layer was formed on the primer layer by the above method, and a sheet was obtained by the same method and tested.

Tensile properties after exposure Measured according to JIS K6301. A primer solution or a photosensitive solution was applied on a glass plate, the solvent was volatilized, and then heat curing was performed at 115 ° C. Then, using a 3kW ultra-high pressure mercury lamp (Oak Seisakusho), use a UV meter (Oak Seisakusho Light Measure Type UV365)
It was exposed for 10 minutes at an illuminance of ² mW / cm ² . Then, the sheet was peeled from the glass plate to obtain a sheet having a thickness of about 100 μm. A 5 mm x 40 mm strip sample was cut from this sheet, and Tensilon RTM-10
0 (manufactured by Orientec Co., Ltd.) and a pulling speed of 20 cn
The initial elastic modulus, 10% stress value, and breaking elongation were measured in 1 / min. When examining the tensile properties of the combined layer of the primer layer and the photosensitive layer, a photosensitive layer was formed on the primer layer by the above method, and a sheet was obtained by the same method and tested.

[Silicone Rubber Layer] The tensile properties of the silicone rubber were measured according to JIS K6301.
After applying silicone rubber liquid to the Teflon plate and drying it,
The sheet was peeled off from the Teflon plate, and a test piece was prepared from the obtained sheet having a thickness of about 300 μm with a No. 4 dumbbell.
The initial elastic modulus, 50% stress value, and breaking elongation may be measured according to SK6301.

Example 1 An aluminum plate having a thickness of 0.3 mm (manufactured by Sumitomo Metal Co., Ltd.) was coated with the following primer composition using a bar coater, and 20
It heat-processed at 0 degreeC for 2 minutes, and provided the 5-micrometer primer layer. (A) Polyurethane resin "Miractran" P22S (manufactured by Nippon Miractolan Co., Ltd.) 100 parts by weight (b) Blocked isocyanate "Takenate B830" (manufactured by Takeda Pharmaceutical Co., Ltd.) 20 parts by weight (c) Epoxy / phenol / urea resin " SJ9372 "(manufactured by Kansai Paint Co., Ltd.) 8 parts by weight (d) titanium oxide 10 parts by weight (e) dibutyltin diacetate 0.5 parts by weight (f) mono (2-methacryloyloxyethyl) acid phosphate 1 part by weight ( g) Dimethylformamide 725 parts by weight

Subsequently, the following photosensitive layer composition was applied onto this primer layer using a bar coater and dried in hot air at 110 ° C. for 1 minute to form a photosensitive layer having a thickness of 1.5 μm. (A) Partial esterification product of 1,2-naphthoquinone-2-diazide-5-sulfonic acid chloride and phenol formaldehyde novolac resin (Sumitomo Durez: "Sumilite Resin" PR50622) (esterification degree 36% by elemental analysis method) 70 parts by weight (b) 4,4'-diphenylmethane diisocyanate 21 parts by weight (c) Polyurethane resin "Samprene" LQ-T1331 (manufactured by Sanyo Chemical Industries, Ltd.) (glass transition point Tg: -37 ° C) 30 parts by weight ( d) Dibutyltin diacetate 0.2 parts by weight (e) P-toluenesulfonic acid 0.8 parts by weight (f) Tetrahydrofuran 800 parts by weight

Then, a silicone rubber composition having the following composition was spin-coated on this photosensitive layer, and then wet-heat cured at 115 ° C., dew point 30 ° C. for 3.5 minutes to form a silicone rubber layer having a thickness of 2 μm. (A) Polydimethylsiloxane (molecular weight of about 25,000, terminal hydroxyl group) 100 parts by weight (b) Vinyltri (methylethylketoxime) silane 10 parts by weight (c) "Isopar" E (manufactured by Exxon Chemical Co., Ltd.) 1400 parts by weight

A 10 μm-thick polypropylene film “Trephan” (manufactured by Toray Industries, Inc.) was laminated on the thus obtained laminate using a calendar roller to obtain a waterless planographic printing plate precursor. .

A metal halide lamp (Idlefin 2000 manufactured by Iwasaki Electric Co., Ltd.) was used as the printing original plate.
The entire surface was exposed for 6 seconds with an illuminance of 11 mW / cm 2 using a UV meter (manufactured by Oak Manufacturing Co., Ltd., Light Measure Type UV-402A).

1 is added to the printing original plate obtained as described above.
A negative film having a halftone dot image of 50 lines / inch was vacuum-contacted and exposed for 60 seconds from a distance of 1 m using the above metal halide lamp.

Then, the "trephan" of the exposed plate was peeled off, and "isopar" H / diethylene glycol dimethyl ether / ethyl cellosolve / N-methyldiethanolamine = 87 / at a temperature of 32 ° C. and a humidity of 80%.
A treatment liquid consisting of 7/3/3 (weight ratio) was applied to the plate surface using a brush. After processing for 1 minute, the processing solution adhering to the plate surface was removed with a rubber squeegee, and then the developing solution (water / butyl carbitol / 2-ethylbutyric acid / crystal violet = 70/30/2 / 0.2 ( (Weight ratio) and lightly rubbing the plate surface with a developing pad, the silicone rubber layer on the image-exposed area was removed, exposing the surface of the photosensitive layer. On the other hand, the non-image area exposed only on the entire surface was covered with the silicone rubber layer. Remained firmly, and an image faithfully reproducing the negative film was obtained.

The obtained printing plate was attached to an offset printing machine (Komori Sprint 4-color machine), and fine quality was obtained using "Dryocolor" ink, indigo, red and yellow ink manufactured by Dainippon Ink and Chemicals, Inc. A printing durability test was conducted by printing on paper.
When 160,000 sheets were printed, good printed matter was printed, and the printing plate after the printing was inspected, but the printing plate was found to be slightly damaged.

The results of measuring the tensile properties of the layers used in this example are shown in Table 2.

Example 2 (Synthesis of diazo resin-1) 14.5 g of p-diazophenylamine sulfate was dissolved in 40.9 g of concentrated sulfuric acid under ice cooling, and 1.0 g of paraformaldehyde was reacted with this solution. The temperature was slowly dropped so that the temperature did not exceed 10 ° C. Thereafter, stirring was continued for 2 hours under ice cooling. The reaction mixture was added dropwise to 500 ml of ethanol under ice cooling, and the resulting precipitate was filtered. 100 ml of precipitate washed with ethanol
Was dissolved in pure water, and a cold concentrated aqueous solution containing 6.8 g of zinc chloride was added to this solution. The generated precipitate was filtered, washed with ethanol, and dissolved in 150 ml of pure water. To this solution was added a cold concentrated aqueous solution in which 8 g of ammonium hexafluorophosphate was dissolved. The resulting precipitate was collected by filtration, washed with water, and dried at 30 ° C. for 24 hours to obtain a diazo resin.

The following primer composition was applied to a 0.24 mm-thick chemical-treated aluminum plate (produced by Sumitomo Metal Co., Ltd.) at 50 ° C. using a whirler and dried at 80 ° C. for 4 minutes to obtain a primer. Layers were provided. (A) Diazo resin-18 8 parts by weight (b) 90 parts by weight of a copolymer resin (Mw = 4.0 × 10 4) having a molar ratio of 2-hydroxyethyl methacrylate and methyl methacrylate of 40/60 (c) γ-methacrylate Roxypropyltrimethoxysilane (Toshiba Silicone) 5 parts by weight (d) Zinc oxide (Sakai Kagaku (manufactured) Fine Zinc Flower) 55 parts by weight (e) "KET-YELLOW 402" (Dainippon Ink and Chemicals, Inc. yellow pigment) ) 12 parts by weight (f) "Nonipol" (Sanyo Kasei Co., Ltd. nonionic surfactant) 5 parts by weight (g) Methyl lactate 700 parts by weight (h) Cyclohexanone 100 parts by weight

After coating and drying, 40 with a metal halide lamp
It was exposed to 0 mJ / cm 2 and dried at 115 ° C. for 5 minutes to form a primer layer having a dry film thickness of 4.5 μm.

Subsequently, the following photosensitive layer composition was coated thereon using a bar coater and dried in hot air at 120 ° C. for 1 minute to form a photosensitive layer having a thickness of 1.5 μm. (A) Partial amidation product of 1,2-naphthoquinone-2-diazide-5-sulfonic acid chloride and 4,4'-diaminobenzophenone (amidation degree by elemental analysis 52%) 55 parts by weight (b) trimethylol Propane triglycidyl ether 30 parts by weight (c) Polyurethane "Samprene" LQ-T1331 (manufactured by Sanyo Chemical Industry Co., Ltd.) (glass transition point Tg: -37 ° C) 20 parts by weight (d) P-toluenesulfonic acid 0.8 Parts by weight (e) 4,4'-diethylaminobenzophenone 3 parts by weight (f) Tetrahydrofuran 800 parts by weight

Then, a silicone rubber composition having the following composition was spin-coated on this photosensitive layer under a dry nitrogen stream, and then wet-heat cured at 115 ° C. and a dew point of 30 ° C. for 3.5 minutes to 2.3 μm. Of the silicone rubber layer. (A) Polydimethylsiloxane (molecular weight about 35,000, terminal hydroxyl group) 100 parts by weight (b) Ethyltriacetoxysilane 12 parts by weight (c) Dibutyltin diacetate 0.1 parts by weight (d) "Isopar" G (exon) Chemical Co., Ltd.) 1200 parts by weight

A polyester film “Lumirror” having a thickness of 8 μm (manufactured by Toray Industries, Inc.) was laminated on the thus obtained laminate using a calendar roller to obtain a waterless planographic printing plate precursor.

A metal halide lamp (Idlefin 2000 manufactured by Iwasaki Electric Co., Ltd.) was used as the printing original plate.
The entire surface was exposed for 6 seconds with an illuminance of 11 mW / cm 2 using a UV meter (manufactured by Oak Manufacturing Co., Ltd., Light Measure Type UV-402A).

1 is added to the printing original plate obtained as described above.
A negative film having a halftone dot image of 50 lines / inch was vacuum-contacted and exposed for 60 seconds from a distance of 1 m using the above metal halide lamp.

Then, the exposed plate "Lumirror" was peeled off, and the TWL116 was prepared under the conditions of room temperature of 25 ° C. and humidity of 80%.
Development was carried out using No. 0 (developing device for waterless planographic printing plate manufactured by Toray Industries, Inc.). Here, as the pretreatment liquid, a liquid having the following composition was used. (A) Diethylene glycol 80 parts by weight (b) Diglycolamine 14 parts by weight (c) Water 6 parts by weight

Water was used as the developing solution. A liquid having the following composition was used as the dyeing liquid. (A) 18 parts by weight of ethyl carbitol (b) 79.9 parts by weight of water (c) 0.1 part by weight of crystal violet (d) 2 parts by weight of 2-ethylhexanoic acid

When the printing plate coming out of the developing device was observed, the silicone rubber layer in the image-exposed portion was removed and the surface of the photosensitive layer was exposed. On the other hand, the silicone rubber layer remained firmly in the non-image portion exposed only to the entire surface, and an image faithfully reproducing the negative film was obtained.

The obtained printing plate was mounted on an offset printing machine (Komori Sprint 4-color machine) and a printing durability test was conducted in the same manner as in Example 1. After printing 170,000 sheets, a good printed matter was printed, and the printing plate after the printing was inspected, but the printing plate was found to be slightly damaged.

The results of measuring the tensile properties of each layer used in this example are shown in Table 2.

Example 3 A 0.24 mm thick aluminum plate (manufactured by Sumitomo Metal Co., Ltd.) was coated with the following primer composition using a slit die coater and heat-treated in hot air at 220 ° C. for 3 minutes to give a thickness of 5 μm. A primer layer was provided. (A) Polyurethane resin "Samprene LQ-T1331" (manufactured by Sanyo Kasei Co., Ltd.) 100 parts by weight (b) Blocked isocyanate "Takenate B830" (manufactured by Takeda Pharmaceutical Co., Ltd.) 20 parts by weight (c) Epoxy phenol Urea resin “SJ9372” (manufactured by Kansai Paint Co., Ltd.) 8 parts by weight (d) Titanium oxide 10 parts by weight (e) Dibutyltin diacetate 0.5 parts by weight (f) Mono (2-methacryloyloxyethyl) acid phosphate 1 Parts by weight (g) dimethylformamide 700 parts by weight (h) tetrahydrofuran 50 parts by weight

Then, a photosensitive solution (A) and a photosensitive solution (B) each composed of the following composition were mixed on the above primer layer immediately before coating, and the mixture was coated by using a slit die coater, and the mixture was heated at 115 ° C. in 1 After drying for a minute, a photosensitive layer having a thickness of 1.5 μm was provided. Photosensitive solution (A) (a) 1,2-naphthoquinone-2-diazide-5-sulfonic acid chloride and a partial esterified product of trihydroxybenzophenone (esterification degree by elemental analysis: 38%) 80 parts by weight (b) polyurethane " Samprene "LQ-T1331 (manufactured by Sanyo Chemical Industry Co., Ltd.) (glass transition point Tg: -37 ° C) 20 parts by weight (c) dibutyltin diacetate 0.2 parts by weight (d) P-toluenesulfonic acid 0.8 Parts by weight (e) Tetrahydrofuran 700 parts by weight Photosensitive solution (B) (a) Isophorone diisocyanate 20 parts by weight (b) Tetrahydrofuran 100 parts by weight

Then, a silicone rubber liquid having the following composition was applied on this photosensitive layer using a slit die coater, and then heat-cured at 120 ° C. for 4 minutes to obtain 1.8 μm.
Of the silicone rubber layer. (A) Polydimethylsiloxane with vinyl groups at both ends (degree of polymerization: up to 700) 100 parts by weight (b) (CH3) 3Si-O- (Si (CH3) 2-O) 30- (SiH (CH3) -O) 10-Si (CH3) 3 10 parts by weight (c) Chloroplatinic acid / methyl vinyl cyclics complex 0.1 parts by weight (d) Acetylacetone alcohol 0.1 parts by weight (e) Polydimethylsiloxane (degree of polymerization ~ 8000) 10 Parts by weight (f) "Isoper" E (manufactured by Exxon Chemical Co., Ltd.) 1000 parts by weight

A polyester film “Lumirror” (manufactured by Toray Industries, Inc.) having a thickness of 8 μm was laminated on the laminated plate obtained as described above using a calender roller in the same manner as in Example 2 to obtain a waterless planographic printing plate. I got the original edition.

After subjecting the printing plate precursor to the same treatment as in Example 2, image exposure was performed using a negative film having a halftone dot image of 150 lines / inch, and development was performed in the same manner as in Example 2. .

A printing durability test was conducted on the obtained printing plate in the same manner as in Examples 1 and 2, and a printing durability of 150,000 sheets was shown.

The results of measuring the tensile properties of the layers used in this example are shown in Table 2.

Comparative Examples 1 to 3 In the same manner as in Example 1 except that the types and blending amounts of the photosensitive layer components (a) (b) (c) in Example 1 were changed as shown in Table 1. Negative waterless lithographic printing plate precursors having various photosensitive layer compositions were prepared. After subjecting the printing plate precursor to the same treatment as in Example 2, image exposure was performed using a negative film having a halftone dot image of 150 lines / inch.
A development and printing durability test were conducted in the same manner as in Example 2. Table 2 shows tensile properties, image reproducibility, and printing durability.

In Comparative Example 1, since the amount of the binder polymer in the photosensitive layer was as small as 8.2 wt%, satisfactory tensile properties could not be exhibited and the photosensitive layer was very hard and brittle. When offset printing was performed, the non-image area was contaminated when 60,000 sheets were printed. When the plate was removed from the printing machine and the stained portion was observed with a microscope, the destruction of the photosensitive layer itself, the destruction of the silicone rubber layer at that portion, and the peeling of the silicone rubber layer were observed.

In Comparative Example 2, since the amount of the binder polymer in the photosensitive layer was 86.5 wt%, which was too large,
The physical properties of the photosensitive layer became too soft. At the same time, satisfactory image reproducibility and developability could not be obtained due to the small amount of photosensitive components, and only a plate in which an image could not be reproduced by image exposure or development, that is, a plate in which development was not possible was obtained. As a result, it was not possible to perform a printing durability test on this edition.

In Comparative Example 3, the amount of the photosensitive group in the photosensitive component was increased, that is, 1,2-naphthoquinone-2-
This is the result of trying to solve this problem by increasing the degree of esterification of the partially esterified product of diazide-5-sulfonic acid chloride and phenol formaldehyde novolak resin to 70%. Although the image reproducibility was slightly improved as compared with Comparative Example 2, the amount of the binder polymer in the photosensitive layer was too large, so that the satisfactory physical properties of the photosensitive layer could not be expressed and the photosensitive component itself was small. However, there was a problem with the SK adhesive strength, and as a result, only a low printing durability of 80,000 sheets was obtained.

Examples 4 to 7 Various photosensitizers were prepared in the same manner as in Example 1 except that the types and blending amounts of the photosensitive layer components (a) and (c) in Example 1 were changed as shown in Table 3. A negative waterless planographic printing plate precursor having a layer composition and tensile properties was prepared. After subjecting the printing plate precursor to the same treatment as in Example 2, image exposure was performed using a negative film having a halftone dot image of 150 lines / inch, and development was performed in the same manner as in Example 2 to obtain a printing plate. Got

The obtained printing plate was attached to an offset printing machine (Komori Sprint 4-color machine), and fine paper was prepared using "Dryocolor" ink, indigo, red, and yellow ink manufactured by Dainippon Ink and Chemicals, Inc. A printing durability test was carried out by printing on.
Table 2 shows the tensile properties, the image reproducibility of the printing plate and the printing durability.

Examples 8 to 16 Various binders were used in the same manner as in Example 1 except that the types and blending amounts of the photosensitive layer components (a) and (c) in Example 1 were changed as shown in Table 4. A negative waterless lithographic printing plate precursor having a polymer was prepared. After subjecting the printing plate precursor to the same treatment as in Example 2, imagewise exposure was performed in the same manner,
A printing plate was obtained by performing development in the same manner. The printing durability test was similarly performed on the obtained printing plate. Table 5 shows the tensile properties, the image reproducibility of the printing plate and the printing durability.

[0172]

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

[Table 7]

[0173]

The present invention provides a photosensitive layer containing at least a quinonediazide compound and a binder polymer on a substrate,
In a waterless planographic printing plate precursor in which ink repellent layers were laminated in this order, the tensile properties of the photosensitive layer were (1) initial elastic modulus: 5 to 50 kgf / mm @ 2, and (2) 10% stress: 0.05 -3.0 kgf / mm @ 2 (3) Elongation at break: By softening to 10% or more, it is possible to provide a waterless lithographic printing plate having excellent image reproducibility and printing durability. Therefore, it can be suitably used in newspaper off-wheel printing fields and commercial off-wheel printing fields where high printing durability is required.

Claims (20)

[Claims] 1. A waterless planographic printing plate precursor comprising a substrate, on which a photosensitive layer containing at least a quinonediazide compound and a binder polymer and an ink repellent layer are laminated in this order, the tensile properties of the photosensitive layer are (1) initial elasticity. Ratio: A waterless planographic printing plate precursor characterized by having physical properties of 5 to 50 kgf / mm @ 2. 2. The waterless planographic printing plate precursor according to claim 1, wherein the tensile properties of the photosensitive layer have the following physical properties: (2) 10% stress: 0.05 to 3.0 kgf / mm 2. 3. The waterless planographic printing plate precursor as claimed in claim 1, wherein the photosensitive layer has the following tensile properties: (3) breaking elongation: 10% or more. 4. A waterless lithographic printing plate precursor obtained by laminating a primer layer, a photosensitive layer containing at least a quinonediazide compound and a binder polymer, and an ink repellent layer on a substrate in this order, and the tensile property of the primer layer is ( 1) Initial elastic modulus: A waterless planographic printing plate precursor having physical properties of 5 to 50 kgf / mm @ 2. 5. The waterless planographic printing plate precursor as claimed in claim 4, wherein the tensile properties of the primer layer are (2) 10% stress: 0.05 to 3.0 kgf / mm @ 2. 6. The waterless lithographic printing plate precursor as claimed in claim 4, wherein the primer layer has the following tensile properties: (3) breaking elongation: 10% or more. 7. A waterless lithographic printing plate precursor comprising a substrate, a primer layer, a photosensitive layer containing at least a quinonediazide compound and a binder polymer, and an ink repellent layer which are laminated in this order on the substrate. The tensile properties of the combined layers are (1) initial elastic modulus: 5 to 50 kgf / mm @ 2, a waterless planographic printing plate precursor. 8. The tensile property of a layer including the primer layer and the photosensitive layer is (2) 10% stress: 0.05 to 3.0 kgf / mm @ 2. Waterless planographic printing plate original. 9. The waterless lithographic printing plate precursor as claimed in claim 7, wherein the tensile properties of the combined layer of the primer layer and the photosensitive layer are (3) elongation at break: 10% or more. . 10. A waterless planographic printing plate precursor comprising a substrate, on which a photosensitive layer containing at least a quinonediazide compound and a binder polymer and an ink repellent layer are laminated in this order, and the tensile property of the photosensitive layer after exposure is (1) ) Initial elastic modulus: A waterless lithographic printing plate precursor having physical properties of 5 to 50 kgf / mm @ 2. 11. The waterless lithographic printing plate as claimed in claim 10, wherein the tensile property of the photosensitive layer after exposure has the physical properties of (2) 10% stress: 0.05 to 3.0 kgf / mm 2. Original version. 12. The waterless lithographic printing plate precursor as claimed in claim 10, wherein the tensile properties of the photosensitive layer after exposure have the following physical properties: (3) breaking elongation: 10% or more. 13. A waterless lithographic printing plate precursor comprising a substrate, a primer layer, a photosensitive layer containing at least a quinonediazide compound and a binder polymer, and an ink repellent layer, which are laminated in this order on the substrate. The waterless planographic printing plate precursor is characterized in that the tensile properties of the combined layers after exposure are (1) initial elastic modulus: 5 to 50 kgf / mm @ 2. 14. The tensile property after exposure of the layer including the primer layer and the photosensitive layer is (2) 10% stress: 0.05 to 3.0 kgf / mm @ 2. The waterless planographic printing plate precursor described in 13. 15. The waterless planographic printing plate according to claim 13, wherein the combined tensile property of the primer layer and the photosensitive layer has the following physical properties: (3) elongation at break: 10% or more. Original printing plate. 16. The binder polymer is contained in the photosensitive layer in a proportion of 15 to 80 wt%.
The waterless planographic printing plate precursor as described in any one of 15 above. 17. A glass transition point (Tg) of the binder polymer.
) Is 0 ° C. or lower.
The waterless planographic printing plate precursor described in any of 1. 18. The waterless lithographic printing plate precursor as claimed in claim 1, wherein the photosensitive layer has a crosslinked structure. 19. The waterless lithographic printing plate precursor as claimed in claim 1, wherein the photosensitive layer is a photo-peeling photosensitive layer. 20. A waterless lithographic printing plate obtained by selectively exposing and developing the waterless lithographic printing plate precursor according to claim 1.