JPH08305009A - Original plate of waterless planographic printing plate - Google Patents

Abstract

PURPOSE: To improve the shelf stability and scratch resistance of an original plate without deteriorating the printing resistance, image reproducibility, etc., by incorporating a compd. having specific structures into the photosensitive layer. CONSTITUTION: This original plate has a photosensitive layer contg. a quinonediazido compd. having a structure represented by the formula -SiRn X3-n , a structure represented by the formula -R1-OH and a structure represented by the formula -Ph(R2)(R3)(R4)(R5)(OH). In the formulae, (n) is an integer of 0-3, R is alkyl, alkenyl, aryl or a group formed by combining such groups, the group represented by R may have a functional group such as halogen, isocyanato or epoxy as a substituent, X is a functional group, R1 is at least. one selected from among S, optionally substd. N, optionally substd. C and optionally substd. Si, Ph is an arom. ring, each of R2-R5 is a substituent and R2-R5 may be different from one another.

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 precursor and a waterless planographic printing plate prepared by selectively exposing and developing the waterless planographic printing plate precursor. The present invention relates to a waterless planographic printing plate precursor having improved storage stability of image reproducibility and a waterless planographic printing plate obtained by selectively exposing and developing the waterless planographic printing plate precursor.

[0002]

2. Description of the Related Art Conventionally, a printing plate for performing lithographic printing using a silicone rubber or a fluororesin as an ink repellent layer without using a fountain solution, particularly a photosensitive lithographic printing plate obtained by selectively exposing and developing. Various editions have been proposed.

For example, as positive-working photosensitive lithographic printing plates, Japanese Patent Publication Nos. 54-26923 and 56-2315 are available.
A waterless planographic printing plate in which a photopolymerizable adhesive layer and a silicone rubber layer which is an ink repellent layer are laminated on a substrate such as No. 0.
Also, Japanese Examined Patent Publication No. 3-56622 and JP-A-61-15365.
No. 5 discloses a waterless lithographic printing plate in which a photodimerization type photosensitive layer and a silicone rubber layer which is an ink repellent layer are laminated on a substrate.

Further, as the negative photosensitive lithographic printing plate,
Waterless lithographic printing in which a photosensitive layer containing a quinonediazide compound is provided on a support, and a silicone rubber layer, which is an ink repellent layer, is provided on the support with a photosensitive layer containing a quinonediazide compound on the support in JP-B-61-616 and JP-B-61-54218. Edition, Japanese Examined Japanese Patent Publication 61-54222
JP-A No. 2003-242242 proposes a waterless planographic printing plate in which a silicone rubber layer, which is an ink repellent layer, is provided on a photoremovable photosensitive layer and is known to have excellent performance in practical use. Among these, in Japanese Patent Publication No. 61-54222, a partially esterified product of 1,2-naphthoquinone-2-diazide-5-sulfonic acid chloride and a phenol novolak resin is crosslinked on a support with a polyfunctional isocyanate. There is disclosed a negative type waterless lithographic printing plate having a photoreleasable photosensitive layer and a silicone rubber layer as an ink repellent layer thereon.

Further, as a photosensitive lithographic printing plate using a fluororesin as an ink repellent layer, there is disclosed in Japanese Patent Laid-Open No. 2-254449.
No. 1, Japanese Patent Laid-Open No. 2-85855, 1H, 1H, 2H,
2H-heptadecafluorodecyl acrylate and 1H,
A waterless lithographic printing plate using a fluororesin containing 1H, 2H, 2H-heptadecafluorodecyl methacrylate as an ink repellent layer is disclosed.

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 ink repellent layer in the non-image area will be damaged, and this will spread to the ink repellent layer and reduce the image reproducibility. Occurs. This result appears as a problem of insufficient printing durability of the printing plate.

Various studies have been made so far for the purpose of improving the printing durability. Japanese Patent Laid-Open No. 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 both cases, not only printing durability is not practically obtained, but also a sufficient primer layer film thickness is required to cover the physical properties of the photosensitive layer, so curing of the primer layer is insufficient. There is a problem that the ink repelling layer is peeled off or the photosensitive layer is peeled off, and in a worse case, the primer layer itself is peeled off from the substrate.

Although a method of thickening the ink repellent layer has been attempted, there is a problem in that the developability is lowered and the ink mileage is lowered.

JP-A-1-154158, JP-A-1-1-1
No. 54159 and the like try to cover a decrease in ink mileage by thickening a silicone rubber layer, which is an ink repellent layer, by adjusting a cell depth by embedding an ink receptive substance. The decrease still exists, and there is a problem that it is practically difficult to handle due to the addition of a new process such as embedding of an ink-carrying substance. In Japanese Patent Laid-Open No. 1-161242,
It has a thick silicone rubber layer obtained by imagewise exposing and developing a plate having an ink inking layer (photosensitive layer) as the uppermost layer, then applying an ink repellent layer (silicone rubber layer) and then further developing. Waterless planographic printing plates have 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, which is an ink repellent layer. Addition of fillers and increase in the molecular weight of polydimethylsiloxane,
No. 32349, a waterless planographic printing plate having a microporous layer containing a cured product of an ink repellent substance, JP-A-2-88.
No. 47 proposes a waterless planographic 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.

JP-A-63-213848 describes a photosensitive layer containing an acrylic acid derivative copolymer. The acrylic acid derivative copolymer is incorporated in the photosensitive layer in an amount of 50.
If it is contained in an amount of more than wt%, there is a problem that the image reproducibility and the adhesiveness to the silicone rubber layer, which is the ink repellent layer, are impaired, and if it is less than 50 wt%, the printing durability becomes 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 a hydroxyphenyl methacrylamide derivative. Those containing a polymer 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.

Japanese Patent Application No. 6-156206 and Japanese Patent Application No. 6-18
3757 and Japanese Patent Application No. 6-183758, the amount of the binder polymer in the photosensitive layer is increased, or the photosensitive layer is softened by using a soft photosensitizer to maintain the developability and image reproducibility. Although it has been made to dramatically improve the printing property, the problem of storage stability of plate performance remained.

[0014]

The present invention was devised in order to improve the various drawbacks of the prior art. By incorporating a compound having a specific structure in the photosensitive layer, the printing durability of the plate can be improved. Without reducing the image reproducibility, etc.
It is intended to provide a waterless planographic printing plate precursor having improved plate storage stability and scratch resistance.

[0015]

The object of the present invention is as follows.
Achieved by the following waterless planographic printing. (1) In a waterless planographic printing plate precursor in which at least a photosensitive layer and a silicone rubber layer are laminated in this order on a support, the photosensitive layer has at least one structure represented by the following general formula (I). A waterless planographic printing plate containing at least one structure represented by the following general formula (II) and at least one quinonediazide compound having at least one structure represented by the following general formula (III) Original printing plate.

—SiR _n X _3-n (I) (In the formula, n is an integer of 0 to 3, and R represents an alkyl group, an alkenyl group, an aryl group, or a group in which these are combined. It may have a functional group such as a halogen atom, an isocyanate group, an epoxy group, an amino group, a hydroxy group, an alkoxy group, an aryloxy group, a (meth) acryloxy group or a mercapto group as a substituent.
Indicates a functional group. ) -R1-OH (II) -Ph (R2) (R3) (R4) (R5) (OH) (III) (In the formula, R1 is a sulfur atom, a substituted or unsubstituted nitrogen atom, a substituted or unsubstituted nitrogen atom, It is at least one selected from the group of carbon atoms and substituted or unsubstituted silicon atoms, Ph is an aromatic ring, and R2, R3, R4, and R5 are substituents, which may be the same or different. First, the configuration of the present invention will be described more specifically.

A feature of the present invention is that in a waterless planographic printing plate precursor in which at least a photosensitive layer and a silicone rubber layer are laminated in this order on a support, the photosensitive layer is represented by the following general formula (I). At least one structure represented by the following general formula (II), and at least one quinonediazide compound having at least one structure represented by the following general formula (III) .

—SiR _n X _3-n (I) (In the formula, n is an integer of 0 to 3, and R is an alkyl group, an alkenyl group, an aryl group, or a group in which these are combined. It may have a functional group such as a halogen atom, an isocyanate group, an epoxy group, an amino group, a hydroxy group, an alkoxy group, an aryloxy group, a (meth) acryloxy group or a mercapto group as a substituent.
Indicates a functional group. As the functional group of X, a hydrogen atom, a hydroxyl group, an alkoxy group, an acyloxy group, a ketoxime group, an amide group, an aminooxy group, an amino group, an alkenyloxy group and the like are shown. ) -R1-OH (II) -Ph (R2) (R3) (R4) (R5) (OH) (III) (In the formula, R1 is a sulfur atom, a substituted or unsubstituted nitrogen atom, a substituted or unsubstituted nitrogen atom, It is at least one selected from the group of carbon atoms and substituted or unsubstituted silicon atoms, Ph is an aromatic ring, and R2, R3, R4, and R5 are substituents, which may be the same or different. By using a soft photosensitizer as in Japanese Patent Application No. 6-183757, the photosensitive layer can be softened, and printing durability can be dramatically improved while maintaining developability and image reproducibility. Adhesion between layer and photosensitive layer (SK adhesion)
It was necessary to add an excessive cross-linking agent (silane coupling agent) into the silicone rubber layer in order to express the above. As a result, the cross-linking agent remained after the plate was prepared, and it reacted with the passage of time, causing a problem in the storage stability of plate performance. Furthermore, the excessive cross-linking agent also adversely affected the physical properties of the silicone rubber layer itself, that is, scratch resistance (scratch resistance).

In the present invention, at least one structure represented by general formula (I), at least one structure represented by general formula (II), and at least one structure represented by general formula (III) By containing at least one novel quinonediazide compound (a silyl group-containing quinonediazide compound), it is possible to effectively and stably develop SK adhesive force without increasing the amount of the crosslinking agent in the silicone rubber layer. Therefore, problems such as storage stability do not occur.

On the other hand, as in JP-A-5-333535, only containing a compound having a structure represented by the general formula (I) in the photosensitive layer results in a rigid structure of the quinonediazide compound in the photosensitive layer. In addition, the photosensitive layer becomes very brittle. Therefore, in addition to the fact that the silicone rubber layer is peeled from the photosensitive layer due to the stress applied to the interface between the silicone rubber layer and the photosensitive layer during printing, cracks occur in the photosensitive layer itself, and it is said that the silicone rubber layer is missing due to the cracks. In some cases, in some cases, the photosensitive layer and the silicone rubber layer may be missing from the primer layer.
The novel quinonediazide compound (silyl group-containing quinonediazide compound) of the present invention has not only one structure represented by the general formula (I) as described above but also at least one structure represented by the general formula (II). , The general formula (II
Since the photosensitive layer itself has a flexible structure having at least one structure represented by I), the problem can be solved.

As a method of preparing the compound, a method of reacting a known silyl group-containing compound with a quinonediazide compound having at least one of the structures of the general formulas (II) and (III) is preferable.

Specific examples of the structure represented by formula (I) include an alkoxysilyl group, an acetoxysilyl group, an oximesilyl group, a trimethylsiloxy group, a triethylsiloxy group and a triphenylsiloxy group. Of these, an alkoxysilyl group, an acetoxysilyl group and an oximesilyl group are preferable.

Specific examples of the alkoxysilyl group include trimethoxysilyl group, triethoxysilyl group, methyldimethoxysilyl group, methyldiethoxysilyl group, vinyldimethoxysilyl group, vinyldiethoxysilyl group, allyldimethoxysilyl group and allyl. Diethoxysilyl group, 3
-Methacryloxypropyldimethoxysilyl group, 3-methacryloxypropyldiethoxysilyl group, dimethylmethoxysilyl group, dimethylethoxysilyl group, divinylmethoxysilyl group, divinylethoxysilyl group, diallylmethoxysilyl group, diallylethoxysilyl group, 3-
Methacryloxypropyl methylmethoxysilyl group, 3-
Methacryloxypropylmethylethoxysilyl group etc.

Specific examples of the acetoxysilyl group include a triacetoxysilyl group, a methyldiacetoxysilyl group,
Ethyldiacetoxysilyl group, dimethyldiacetoxysilyl group, diethylacetoxysilyl group, etc.

Specific examples of the oxime silyl group include a triketoxime silyl group, a methyldiketoxime silyl group, and an ethyl ketoxime silyl group.

As the silyl group-containing compound for introducing the structure represented by the general formula (I) into the quinonediazide compound, known alkoxysilane, acetoxysilane,
Examples include oxime silane, amino silane and amido silane.

Of these silyl group-containing compounds, reactive group-containing silyl compounds are preferred. As the reactive alkyl group-containing silyl compound, a chloroalkylsilyl compound,
Epoxy alkyl silyl compounds, amino alkyl silyl compounds, mercapto alkyl silyl compounds, isocyanate alkyl silyl compounds and the like. Examples of the silyl compound containing a polymerization reactive group include methacryloxy alkyl silyl compounds, acryloxy alkyl silyl compounds, and styryl silyl compounds. , Vinyl ester silyl compounds, alkenyl silyl compounds and the like.

Specific examples of the chloroalkylsilyl compound include bis (chloromethyl) dimethylsilane, bromomethyltrimethylsilane, 3-bromopropyltrimethoxysilane, 4-bromotrimethylsiloxybenzene and 2
-Chloroethyltriethoxysilane, chloromethyldimethylethoxysilane, chloromethyldimethylphenylsilane, chloromethylmethyldiethoxysilane, p- (chloromethyl) phenyltrimethoxysilane, chloromethyltriethoxysilane, chlorophenyltritriethoxysilane, 3- Examples thereof include chloropropylmethyldimethoxysilane, 3-chloropropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 1-trimethoxysilyl-2- (p, m-chloromethyl) phenylethane and the like.

Specific examples of the epoxyalkylsilyl compound include 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyldimethylethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyl. Trimethoxysilane, 3
-(N-allyl-N-glycidyl) aminopropyltrimethoxysilane, N-glycidyl-N, N-bis [3-
(Methyldimethoxysilyl) propyl] amine, N-glycidyl-N, N-bis [3- (trimethoxysilyl)
Propyl] amine and the like.

Specific examples of the aminoalkylsilyl compound include 4-aminobutyldimethylmethoxysilane and 4-aminobutyldimethylmethoxysilane.
Aminobutyltriethoxysilane, 4-aminobutyltrimethoxysilane, (aminoethylaminomethyl) phenethyltrimethoxysilane, N- (2-aminoethyl)-
3-aminopropylmethylmethyldimethoxysilane, N
-(2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltris (2-ethylhexoxy) silane, 6-
(Aminohexylaminopropyl) trimethoxysilane, p-aminophenyltrimethoxysilane, 3- (1
-Aminopropoxy) 3,3-dimethyl-1-propenyltrimethoxysilane, 3-aminopropyltris (methoxyethoxyethoxy) silane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyl Trimethoxysilane,
3-aminopropyltris (trimethylsiloxy) silane, 1-trimethoxysilyl-2- (pm-aminomethyl) phenylethane, trimethoxysilylpropyldiethylenetriamine and the like can be mentioned.

Specific examples of the mercaptoalkylsilyl compound include 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane and 3
-Mercaptopropyltriethoxysilane and the like.

Specific examples of the isocyanate alkylsilyl compound include 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropyldimethylchlorosilane and 3-isocyanatopropyltrimethoxysilane.

Typical examples of the silyl compound having a polymerizable reactive group include vinyltrimethoxysilane, hexenyltrimethoxysilane, styryltrimethoxysilane and 3
-Methacryloxypropyltrimethoxysilane, 3-methacryloxypropyldimethylethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltris (methoxyethoxy) silane, 7-octenyltrimethoxysilane, phenylvinyldimethoxy Examples thereof include silane, m, p-styrylethyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, N, N-dimethylaminovinyldiethoxysilane and diphenylvinylethoxysilane.

Other reactive group-containing silyl compounds include 2-cyanoethyltriethoxysilane, (cyanomethylphenethyl) triethoxysilane, 3-cyanopropyltriethoxysilane, N- (triethoxysilylpropyl) dansylamide, N -[3- (triethoxysilyl) propyl] -2,4-dinitrophenylamide,
Triethoxysilylpropyl ethyl carbamate, N-
[3- (triethoxysilyl) propyl] phthalamic acid, triethoxysilylpropyl-p-nitrobenzamide, N- (triethoxysilylpropyl) urea, 2-
(Trimethoxysilyl) ethylphenylsulfonyl azide, β-trimethoxysilylethyl-2-pyridine, N
-(Trimethoxysilylpropyl) imidazole and the like can be mentioned.

Further, a silyl group-containing compound represented by the following general formula (IV) can also be used.

[0036]

Embedded image (R6: carbon, oxygen, a divalent linking group consisting of a nitrogen, for example, _{-C 3 H 6 -, - C} 3 H 6 -NH-C 3 H 6
-Etc. ) R7: an alkyl group having 1 to 3 carbon atoms or a phenyl group X: similar to the general formula (I), a = 1 to 2, n = 1 to 3) at least one of the structures of the general formulas (II) and (III), respectively. The quinonediazide compounds each having are disclosed in Japanese Patent Application No. 6-
According to the method described in 183757, it can be obtained by reacting a compound having at least one structure represented by each of the general formulas (II) and (III) with a quinonediazide compound.

Specific examples of R1 in the general formula (II) include:
Hydrogen atom, halogen atom, hydroxyl group, nitro group, amino group, mercapto group, cyano group, sulfonyl group, nitroso group, substituted or unsubstituted alkyl group having 1 to 100 carbon atoms, alkoxy group, amide group, acyloxy group, alkanoyl Group, formyl group, carboxyl group, carbon number 2
At least one selected from the group consisting of 100 substituted or unsubstituted alkenyl groups, alkenyloxy groups, substituted or unsubstituted aryl groups having 4 to 100 carbon atoms, and aryloxy groups is included, but is not limited thereto. .

Further, R2, R3 and R in the general formula (III) are
4, specific examples of R5 include a hydrogen atom, a halogen atom,
Hydroxyl group, nitro group, amino group, mercapto group, cyano group, sulfonyl group, nitroso group, substituted or unsubstituted alkyl group having 1 to 100 carbon atoms, alkoxy group, amide group, acyloxy group, alkanoyl group, formyl group,
Carboxyl group, substituted or unsubstituted alkenyl group having 2 to 100 carbon atoms, alkenyloxy group, 4 to 1 carbon atoms
00 is at least one selected from the group consisting of a substituted or unsubstituted aryl group and an aryloxy group, which may be the same or different and are not limited to these and may be other.

The structure represented by the general formula (II) and the general formula (II
Examples of the compound having at least one structure represented by I) include, but are not limited to, the following compounds.

A compound having a skeleton obtained by the reaction of an epoxy compound with phenol benzoic acid, as represented by the following general formula (V). For example, a reaction product of 1,2-epoxypropane and 2-hydroxybenzoic acid or 1,2-
Reaction product of epoxypropane and 3-hydroxybenzoic acid, reaction product of 1,2-epoxypropane and 4-hydroxybenzoic acid, reaction product of 1,2-epoxybutane and 2-hydroxybenzoic acid, 1,2 -Epoxy butane and 3-
Reaction product with hydroxybenzoic acid, reaction product with 1,2-epoxybutane and 4-hydroxybenzoic acid, reaction product with 2,3-epoxybutane and 2-hydroxybenzoic acid, 2,
Reaction product of 3-epoxybutane and 3-hydroxybenzoic acid, reaction product of 2,3-epoxybutane and 4-hydroxybenzoic acid, reaction product of 1,2-epoxyhexane and 2-hydroxybenzoic acid, 1 , 2-epoxyhexane and 3
Reaction product with -hydroxybenzoic acid, reaction product with 1,2-epoxyhexane and 4-hydroxybenzoic acid, 1,2,
Reaction product of 3,4-diepoxybutane and 2-hydroxybenzoic acid, reaction product of 1,2,3,4-diepoxybutane and 3-hydroxybenzoic acid, 1,2,3,4-diepoxy Reaction products of butane and 4-hydroxybenzoic acid, reaction products of glycidyl acrylate and 2-hydroxybenzoic acid and homopolymers and copolymers thereof, glycidyl acrylate and 3-hydroxybenzoic acid Reactants and their homopolymers and copolymers, glycidyl acrylate and 4-
Reaction products with hydroxybenzoic acid and homopolymers and copolymers thereof, reaction products with glycidyl methacrylate and 2-hydroxybenzoic acid and homopolymers and copolymers thereof,
Reaction product of glycidyl methacrylate with 3-hydroxybenzoic acid and homopolymer or copolymer thereof, reaction product of glycidyl methacrylate with 4-hydroxybenzoic acid and homopolymer or copolymer thereof, etc. However, the present invention is not limited to these, and any reaction product of a compound having an epoxy group and phenol benzoic acid may be used. The molecular weight of the compound having an epoxy group is not particularly limited, but a molecular weight of 60 to 10,000,000 is preferable, and a molecular weight of 80 to 1,000,000 is more preferable.

[0041]

Embedded image (Ph, R2, R3, R4, and R5 in the formula are represented by the general formula (III
), Ph, R2, R3, R4, and R5. ) A compound having a skeleton obtained by the reaction of triol or polyol with hydroxybenzaldehyde as represented by the following general formula (V). For example, 1, 2,
Reaction product of 4-butantryol with 2-hydroxybenzaldehyde, reaction product of 1,2,4-butantryol with 3-hydroxybenzaldehyde, reaction product of 1,2,4-butantryol with 4-hydroxybenzaldehyde Reaction product, reaction product of glycerin and 2-hydroxybenzaldehyde, reaction product of glycerin and 3-hydroxybenzaldehyde, reaction product of glycerin and 4-hydroxybenzaldehyde, reaction product of trimethylolpropane and 2-hydroxybenzaldehyde, trimethylol -Reaction product of propane and 3-hydroxybenzaldehyde, reaction product of trimethylolpropane and 4-hydroxybenzaldehyde, reaction product of polyvinyl alcohol and 2-hydroxybenzaldehyde, polyvinyl alcohol and 3-hydroxyl A reaction product of benzaldehyde, polyvinyl alcohol - le and 4-hydroxybenzaldehyde reaction product of it is like, but are not limited to,
Any reaction product of triol or polyol and hydroxybenzaldehyde may be used. The molecular weight of triol or polyol is not particularly limited, but a molecular weight of 90 to 10,000,000 is preferable, and a molecular weight of 90 to 1,000,000 is more preferable.

[0042]

Embedded image (Ph, R2, R3, R4, and R5 in the formula are represented by the general formula (III
), Ph, R2, R3, R4, and R5. R
8 is a sulfur atom, a substituted or unsubstituted nitrogen atom, a substituted or unsubstituted silicon atom, a substituted or unsubstituted alkyl group having 1 to 100 carbon atoms, an alkoxy group, an amide group, an acyloxy group, an alkanoyl group, a formyl group. , Carboxyl group, substituted or unsubstituted alkenyl group having 2 to 100 carbon atoms, alkenyloxy group, 4 to 10 carbon atoms
Examples thereof include, but are not limited to, a 0-substituted or unsubstituted aryl group and an aryloxy group. ) A compound having a skeleton represented by the following general formula (VII). For example, 2- (2-hydroxyethyl) pheno-
3- (2-hydroxyethyl) phenol, 4-
(2-hydroxyethyl) phenol, 2- (1-hydroxyethyl) phenol, 3- (1-hydroxyethyl) phenol, 4- (1-hydroxyethyl) phenol, 2- (3 -Hydroxypropyl) phenol, 3
-(3-hydroxypropyl) phenol, 4- (3-
Hydroxypropyl) phenol, 2- (2-hydroxypropyl) phenol, 3- (2-hydroxypropyl) phenol, 4- (2-hydroxypropyl) phenol, 2- (6-hydroxyhexyl) ) Pheno-
3- (6-hydroxyhexyl) phenol, 4-
Examples thereof include (6-hydroxyhexyl) phenol, but are not limited thereto. The molecular weight of such a compound is not particularly limited, but one having a molecular weight of 120 to 10,000,000 is preferable, and one having a molecular weight of 120 to 1,000,000 is more preferable.

HO-R9-Ph (R2) (R3) (R4) (R5) (OH) (VII) (Ph, R2, R3, R4 and R5 in the formula are represented by the general formula (II
I) the same as Ph, R2, R3, R4 and R5. R
9 is a sulfur atom, a substituted or unsubstituted nitrogen atom, a substituted or unsubstituted silicon atom, a substituted or unsubstituted alkyl group having 1 to 100 carbon atoms, an alkoxy group, an amide group, an acyloxy group, an alkanoyl group, a formyl group. , Carboxyl group, substituted or unsubstituted alkenyl group having 2 to 100 carbon atoms, alkenyloxy group, 4 to 10 carbon atoms
Examples thereof include, but are not limited to, a 0-substituted or unsubstituted aryl group and an aryloxy group. ) A compound having a skeleton represented by the following general formula (VIII). Examples thereof include, but are not limited to, a copolymer of hydroxyethyl acrylate and hydroxystyrene, a copolymer of vinyl acetate and hydroxyethyl methacrylate, and a copolymer of hydroxystyrene. The molecular weight of such a compound is not particularly limited, but a molecular weight of 300 to
10 million is preferable, and molecular weight is 1000-100
Thousands are more preferable.

[0044]

[Chemical 4] (Ph, R2, R3, R4, and R5 in the formula are represented by the general formula (II
I) the same as Ph, R2, R3, R4 and R5. R
10 and R11 represent a polymer main chain, and include a sulfur atom, a substituted or unsubstituted nitrogen atom, a substituted or unsubstituted silicon atom, a substituted or unsubstituted alkyl group having 1 to 10 million carbon atoms, and an alkoxy group. , Amide group, acyloxy group, alkanoyl group, formyl group, carboxyl group, substituted or unsubstituted alkenyl group having 2 to 10 million carbon atoms, alkenyloxy group, substituted or unsubstituted aryl group having 4 to 10 million carbon atoms Groups, aryloxy groups, and the like, but are not limited thereto. ) Each of these compounds such as or a compound having at least one of the structures represented by the general formula (II) and the structure represented by the general formula (III) is used alone, or two or more of them are quinonediazide compounds. The structure represented by the general formula (II) and the general formula (II
A compound having at least one structure represented by I) can be obtained.

By reacting this with the above-mentioned silyl group-containing compound, another desired compound can be obtained.

Examples of the quinonediazide compound in the present invention include, but are not limited to, benzoquinonediazidesulfonic acid and its derivative, naphthoquinonediazidesulfonic acid and its derivative, and the like. Specifically, 1,2-benzoquinone-2-diazido-4-sulfonic acid chloride, 1,2-benzoquinone-2-diazido-4-sulfonic acid bromide, 1,2-benzoquinone-2
-Diazido-4-sulfonic acid sodium salt, 1,2-benzoquinone-2-diazido-4-sulfonic acid potassium salt, 1,2-benzoquinone-2-diazido-4-sulfonic acid, 1,2-naphthoquinone-2-diazido-4-sulfonic acid chloride, 1,2-naphthoquinone-2-diazido-4-sulfonic acid bromide, 1,2-naphthoquinone-2
-Diazido-4-sulfonic acid sodium salt, 1,2-naphthoquinone-2-diazido-4-sulfonic acid potassium salt, 1,2-naphthoquinone-2-diazido-4-sulfonic acid, 1,2-naphthoquinone-2-diazido-5-sulfonic acid chloride, 1,2-naphthoquinone-2-diazido-5-sulfonic acid bromide, 1,2-naphthoquinone-2
-Diazido 5-sulfonic acid sodium salt, 1,2-naphthoquinone-2-diazido 5-sulfonic acid potassium salt, 1,2-naphthoquinone-2-diazido 5-sulfonic acid, 1,2-naphthoquinone-2-diazido 6-sulfonic acid chloride, 1,2-naphthoquinone-2-diazido 6-sulfonic acid bromide, 1,2-naphthoquinone-2
-Diazido 6-sulfonic acid sodium salt, 1,2-naphthoquinone-2-diazido 6-sulfonic acid potassium salt, 1,2-naphthoquinone-2-diazido 6-sulfonic acid and the like, but not limited to these, It may be one. Among these, 1,2-naphthoquinone-2-diazide sulfonic acid and its derivatives, especially 1,2-naphthoquinone-2-diazido-4-sulfonic acid chloride, 1,2-naphthoquinone-2-diazido-5
-Sulfonic acid chloride, 1,2-naphthoquinone-2-diazido-4-sulfonic acid sodium salt, and 1,2-naphthoquinone-2-diazido5-sulfonic acid sodium salt are effective.

The reaction of these quinonediazide compounds with a compound having at least one structure represented by the general formula (II) and at least one structure represented by the general formula (III) is usually an esterification reaction. preferable. Therefore, the target reaction product has a sulfonate structure. For example, when a copolymer of hydroxyethyl acrylate and hydroxystyrene is reacted with 1,2-naphthoquinone-2-diazido-4-sulfonic acid chloride, the hydroxyl portion and the sulfonic acid chloride portion of the copolymer are It reacts and becomes a sulfonate while removing hydrochloric acid.

The structure represented by the general formula (II) and the general formula (II
The reaction ratio of the compound having at least one of the structure represented by I) and the quinonediazide compound is not particularly limited, but preferably the structure represented by the general formula (II) and the structure represented by the general formula (III) are 0.01 to 1,000,000 parts by weight of a quinonediazide compound based on 100 parts by weight of a compound having at least one of the above, and more preferably the structure represented by the general formula (II) and the structure represented by the general formula (III). The quinonediazide compound is added to 100 parts by weight of the compound having at least one each.
It is preferably obtained by reacting 1 to 100,000 parts by weight.

Further, by reacting these compounds with the above-mentioned silyl group-containing compound, the desired compound can be obtained. Regarding the reaction ratio,
The amount of the silyl group-containing compound is 1 to 1000 parts by weight, preferably 5 to 500 parts by weight, based on 100 parts by weight of the quinonediazide compound having the structure represented by the general formulas (II) and (III).

In the present invention, the silyl group-containing quinonediazide compound obtained as described above is used as an essential component, but a known quinonediazide compound is separately added for the purpose of improving the image reproducibility of the plate or for the purpose of improving it. You may. In that case, the skeletons constituting the quinonediazide compound containing a silyl group and the quinonediazide compound containing no silyl group may be different or the same. Further, even when the skeletons constituting the quinonediazide compound are the same, the amount of quinonediazide groups in the compound may be different.

The tensile properties of the photosensitive layer after exposure are (1) initial elastic modulus: 5 to 50 kgf / mm ² (2) 10% stress: 0.05 to 3.0 kgf / mm ² (3) breaking elongation Degree: It is preferable to have physical properties such as 10% or more.

In the present invention, the initial elastic modulus of the tensile properties of the photosensitive layer is 5 kgf / mm ² or more and less than 50 kgf / mm ² , preferably 7 kgf / mm ² or more and less than 45 kgf / mm ² , and more preferably 10 kgf / mm ² or more and 40 kg.
It is important to make it less than f / mm ² .

The 10% stress value is 0.05 kgf /
mm ² or more and less than 3.0 kgf / mm ² , preferably 0.
1 kgf / mm ² or more and less than 2.0 kgf / mm ² , more preferably 0.1 kgf / mm ² or more and 1.5 kgf /
It is important to make it less than mm ² .

If the initial elastic modulus is less than 5 kgf / mm ² and the 10% stress value is less than 0.05 kgf / mm ² , the photosensitive layer becomes sticky and becomes a cause of stickiness during printing.

Further, it is important to design the tensile properties of the photosensitive layer after exposure, the primer layer, or a layer in which both layers are combined to have a breaking elongation of 10% or more, preferably 15% or more. When the elongation at break is 10% or less, these layers become brittle, and when offset printing is performed, these layers are broken and high printing durability cannot be obtained.

When the initial elastic modulus is 50 kgf / mm ² or more and the elongation at break is 10% or less, for example, Japanese Patent Publication No. 61-542.
Since the photosensitive layer described in Example 1 of No. 22 is a hard photosensitive layer having an initial tensile elastic modulus of 56 kgf / mm ² and an elongation at break of 5.0%, the photosensitive layer and the ink repellent layer when offset printing is performed. A stress is repeatedly applied between the photosensitive layer and the photosensitive layer, and the photosensitive layer itself is destroyed, and subsequently, the adhesive interface with the ink repellent layer is destroyed, and high printing durability cannot be obtained.

The tensile properties of the photosensitive layer after exposure are determined according to JIS K
6301 can be measured. An example of the measuring method is shown below. A photosensitive solution is applied on a glass plate, the solvent is volatilized, and then heat curing is performed at 115 ° C. After that, using a 3 kW ultra-high pressure mercury lamp (Oak Seisakusho),
UV Meter (Oak Seisakusho Light Measure Type U
V365) and expose for 10 minutes at an illuminance of 12 mW / cm ² . After this, peel off the sheet from the glass plate to obtain about 10
A photosensitive layer sheet having a thickness of 0 micron is obtained. A 5 mm × 40 mm strip-shaped sample is cut 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 cm / min.

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 photosensitive layer sheet. 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 of the present invention is usually a light-peeling photosensitive layer. The photoremovable photosensitive layer means a layer in which the ink repellent layer thereon is removed by developing, without substantially removing the exposed photosensitive layer. It is obtained by cross-linking with a known polyfunctional compound or by modifying the active group in the quinonediazide compound with a monofunctional compound to make it insoluble or insoluble in a developing solution.
On the contrary, when these crosslinking and modification are not performed, the exposed portion of the photosensitive layer is removed together with the ink repellent layer during development.

Examples of the polyfunctional compound used for introducing the crosslinked structure include the following polyfunctional isocyanates and polyfunctional epoxy compounds, but are not limited thereto.

Examples of polyfunctional isocyanates include paraphenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI) and tolidine diisocyanate. (TODI), 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 (H12 MDI) (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), tetramethyl xylylene diisocyanate, polymethylene polyphenyl isocyanate, dimer acid diisocyanate (DDI), triphenylmethane triisocyanate, tris (isocyanatophenyl) thiophosphate, tetramethyl xylylene diisocyanate, lysine ester triisocyanate, 1, 6, 11
-Undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyl octane, 1,3
Examples thereof include, but are not limited to, 6-hexamethylene triisocyanate, bicycloheptane triisocyanate and the like, polyisocyanate polyhydric alcohol adducts, and polyisocyanate polymers. Polyfunctional epoxy compounds include polyethylene glycol diglycidyl ethers, polypropylene glycol diglycidyl ethers, bisphenol A diglycidyl ether, trimethylolpropane triglycidyl ether.
Tel and the like, but are not limited thereto. Preferred among these 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 with respect to 100 parts by weight of the photosensitive compound.

The heat curing is preferably carried out at a temperature which does not lose the photosensitivity of the photosensitive material, usually at 150 ° C. or lower. For this reason, it is preferred to use a known catalyst in combination.

As a method of modifying a quinonediazide compound by reacting it with a monofunctional compound to make it hardly soluble or insoluble in a developing solution, similarly, the active group of the photosensitive compound is esterified, amidated or urethanized. There are things to do. The compound that reacts with the active group of the photosensitive 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 which retains the shape of the photosensitive layer in the present invention, any binder polymer capable of forming an organic solvent and capable of forming a film can be used, but its glass transition temperature (Tg) is preferable. ) Is 20 ℃
The following polymers and copolymers, and more preferably polymers and copolymers having a glass transition temperature (Tg) of 0 ° C. or less 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. Conventionally, a dilatometer is used to measure the volume of a sample while raising the temperature, and it is determined 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 to these and other polymers may be used.

(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, methacryl Acid n-hexyl, lauryl methacrylate, acrylic acid,
Methacrylic acid, maleic acid, itaconic acid, methacrylic acid-2-hydroxyethyl, methacrylic acid-2-hydroxypropyl, acrylic acid-2-hydroxyethyl, acrylic acid-2-hydroxypropyl, 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 chromatography cyanoacrylate 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)
Ethers, glycerin, trimethylolethane, trimethylolpropane, and other polyfunctional alcohols with ethylene oxide and propylene oxide added and then (meth) acrylated, and polymers and copolymers obtained by polymerizing and copolymerizing these derivatives. Can be used as a binder polymer.

Specific examples of the vinyl-based polymer having a glass transition temperature of 20 ° C. or lower include, but 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-dimethylbutene), poly (1,1-dimethylpropene), poly (1dodecene), polyethylene, poly (1-heptene), poly (1-hexene), polymethylene, poly (6-methyl-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 20 ° C. or lower include poly (4-[(2-butoxyethoxy) methyl] styrene), poly (4-decylstyrene), poly (4dodecylstyrene). , Poly [4- (2-ethoxyethoxymethyl) styrene], poly [4- (1-ethylhexyloxymethyl) styrene], poly [4- (hexyloxymethyl) styrene], poly (4-hexylstyrene), Examples thereof include poly (4-nonylstyrene), poly [4- (octyloxymethyl) 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 20 ° C. or lower include, for example, poly (butyl acrylate), poly (sec-butyl acrylate), poly (tert-butyl acrylate), and poly [tert-butyl acrylate]. 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-ethylthiopropyl 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-methylthioethyl 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 are typical examples.

Examples of polymethacrylates having a glass transition temperature of 20 ° C. or lower are, for example, poly (decyl methacrylate), poly (dodecyl methacrylate), poly (2-ethylhexyl methacrylate), poly (octadecyl methacrylate), poly (octyl methacrylate), poly (octyl methacrylate). (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, methacrylic acid Ester-butadiene copolymer, acrylic ester-acrylonitrile copolymer (ANM), isobutylene-isoprene copolymer (IIR), acrylonitrile-butadiene copolymer (NBR), carboxy-modified acrylonitrile-butadiene copolymer, ac Lilonitrile-chloroprene copolymer, acrylonitrile-isoprene copolymer, ethylene-propylene copolymer (EP
M, EPDM), vinyl pyridine-styrene-butadiene copolymer, styrene-isoprene copolymer and the like.

In addition to these, specific examples of rubbers having a glass transition temperature of 20 ° C. or lower include, 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-1,1)
3-butadiene), poly (2-isopropyl-1,3-)
Butadiene), poly (2-methyl-1,3-butadiene), chlorosulfonated polyethylene, and the like are included, 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, epoxy Cyclohexane, epoxycycloheptane, epoxycyclooctane, styrene oxide, 2-phenyl-1,2-epoxypropane, tetramethylethylene oxide, epichlorohydrin, epibromohydrin, allyl glycidyl ether, phenyl glycidyl ether, n-butyl glycidyl ether, 1 Ring-opening polymerization of 1,4-dichloro-2,3-epoxybutane, 2,3-epoxypropionaldehyde, 2,3-epoxy-2-methylpropionaldehyde, 2,3-epoxydiethylacetal, etc. More polymers and copolymers can also be used as binder polymers.

Specific examples of the polyoxides having a glass transition temperature of 20 ° 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 acid 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- Le, dipentaerythritol, sorbitol and the like.

Examples of the polyvalent carboxylic acid and the polyvalent carboxylic 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.

Poly (oxydiethylenepimelate), poly (oxydiethylenepropylmalonate), poly (oxydiethylenesebacate), poly (oxydiethylenesuberate), poly (oxydiethylenesuccinate), poly (pentamethylene) Adipate), poly (tetramethylene adipate), poly (tetramethylene sebacate), poly (trimethylene adipate), and the like, but are not limited thereto.

(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) and 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), tetramethyl xylylene diisocyanate, polymethylene polyphenyl isocyanate, dimer acid diisocyanate (DDI), triphenylmethane triisocyanate, tris (isocyanatophenyl) thiophosphate, tetramethyl xylylene diisocyanate, lysine ester triisocyanate, 1, 6, 11
-Undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyl 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. Polypropylene adipate, polypropylene adipate, polyhexamethylene adipate, polyneopentyl adipate,
Examples thereof include polyhexamethylene neopentyl adipate, polyethylene hexamethylene adipate, and the like, and poly-ε-caprolactone diol, polyhexamethylene carbonate diol, polytetramethylene adipate, sorbitol, methyl glucogit, sucrose, and the like.

Various phosphorus-containing polyols, halogen-containing polyols and the like can also 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.

(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-caprolactam, ω-aminoundecanoic acid, hexamethylenediamine, 4,4'-bis-aminocyclohexylmethane,
2,4,4-trimethylhexamethylenediamine, isophoronediamine, diglycols, isophthalic acid, adipic acid, sebacic acid, dodecanedioic acid and the like.

More specifically, polyamides are generally classified into water-soluble polyamides and alcohol-soluble polyamides. As the water-soluble polyamide, for example, a polyamide containing a sulfonic acid group or a sulfonate group obtained by copolymerizing sodium 3,5-dicarboxybenzenesulfonate as disclosed in JP-A-48-72250, 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, and a cyclic amide as disclosed in JP-A-49-43465. Polyamides containing basic nitrogen obtained by copolymerizing N, N'-di (γ-aminopropyl) piperazine and the like as disclosed in JP-A-50-7605 and acrylic acid, etc. Quaternized polyamide, JP-A-55-74537
Copolymerized polyamide containing a polyether segment having a molecular weight of 150 to 1500, and ring-opening polymerization of α- (N, N'-dialkylamino) -ε-caprolactam or α- (N, N ' Examples thereof include polyamides obtained by ring-opening copolymerization of -dialkylamino) -ε-caprolactam and ε-caprolactam.

As the copolyamide containing a polyether segment having a molecular weight of 150 to 1500, polyoxyethylene having an amino group at the terminal and a polyether segment portion having a molecular weight of 150 to 1500 and an aliphatic dicarboxylic acid or diamine are used. From 30 to 30 units
An example of the copolymerized polyamide is 70% by weight.

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 their derivatives, 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.

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

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

Further, the binder polymer may be used in any proportion as long as the photosensitive layer has image reproducibility, but in order to sufficiently bring out the tensile properties of the photosensitive layer in the present invention, it is selected as a component of the photosensitive layer. It is suitable to use 10 to 90 wt%, more preferably 15 to 65 wt%
%, Most preferably 20-55 wt%.

When a quinonediazide sulfonic acid ester is used and the esterification rate is less than 10%, the number of photosensitive groups is small, which causes a problem of deterioration in image reproducibility and developability. On the other hand, when the esterification rate is higher than 90%, it means that the residual hydroxyl group, that is, the number of cross-linking points is decreased, which may cause a problem in the solvent resistance of the photosensitive layer and the adhesive force between the ink repellent layer and the photosensitive layer. is there.

When the content of the binder polymer is less than 10% 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 90% by weight, it means that the amount of the photosensitive compound is decreased. This causes problems in image reproducibility, developability, adhesion between the ink repellent layer and the photosensitive layer, and the like.

In addition to the above-mentioned components, it is optional to add additives such as a photosensitizer, an acid, a base, a dye, a pigment, a photocoloring agent, a surfactant and a catalyst, if necessary. In particular, in order to improve the plate inspection property of the exposed and developed printing plate, a printing plate precursor excellent in visible image reproducibility can be obtained by using appropriate dyes, pigments, photochromic agents, etc., alone or in combination of two or more kinds. Can be.

The thickness of the photosensitive layer is 0.1 to 100 μm, 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.

The support used in the present invention may be any of those used in ordinary waterless lithographic 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, metal plates made of aluminum, copper, zinc, steel, etc., and metal plates plated or vapor-deposited with chromium, zinc, copper, nickel, aluminum, iron, etc., polyethylene terephthalate, polyethylene naphthalate. Plastic film or sheet such as polyethylene, polystyrene, polypropylene, etc., a support having rubber elasticity such as chloroprene rubber, NBR, or a support having such rubber elasticity, or paper, resin-coated paper, Examples include paper coated with a metal foil such as aluminum. It is also possible to coat other substances on these supports for the purpose of preventing halation and for using them as a support.

Of these, a metal plate is preferable,
A metal plate made of aluminum is particularly preferable. Such a metal plate may be used as it is, or may be made into a plane by degreasing treatment with an alkaline aqueous solution or the like before use. Alternatively, the grain shape may be formed by a mechanical method, an electrolytic etching method, or the like. At this time, it is optional to perform the degreasing treatment before forming the grain shape.

In the waterless lithographic printing plate of the present invention, the adhesion between the support and the photosensitive layer is very important for basic plate performance such as image reproducibility and printing durability. Before applying the photosensitive layer, it is preferable to provide a primer layer on the support in order to obtain sufficient adhesion between the photosensitive layer and the support.

The primer layer preferably contains the following binder polymer described in the photosensitive layer as a component.

(1) Vinyl Polymers (a) Polyolefins (b) Polystyrenes (c) Acrylic Ester Polymers and Methacrylic Acid Ester Polymers (2) Unblended Rubber (3) Polyoxides (Polyethers) ( 4) Polyesters (5) Polyurethanes (6) Polyamides In addition to these, the following binder polymers can be used, but the binder polymers are not limited to these and may be other than these.

Urea resins, phenolic resins, benzoguanamine resins, phenoxy resins, diazo resins, cellulose and its derivatives, cellulose and its derivatives, chitin, chitosan, milk casein, gelatin, soybean protein, albumin and the like.

These binder polymers can be used alone or in admixture of two or more, and can be used together with the crosslinking agent described in the photosensitive layer.

Among these, acrylic acid ester polymers and methacrylic acid ester polymers, unripened rubber,
It is preferable to use polyurethane resins, polyoxides, urea resins, diazo resins, milk kagain, gelatin, etc., alone or in admixture with other binder polymers. In particular, it is preferable to use acrylic acid ester polymers and methacrylic acid ester polymers, unblended rubbers, polyurethane resins, polyoxides, urea resins and the like, alone or in a mixture with other binder polymers.

The binder polymer may be used in any ratio as long as it can bond the support and the photosensitive layer, but it is contained in the primer layer component of the present invention in an amount of 5 to 10.
It is preferable to use 0 wt%, more preferably 10 to 9
9 wt%, most preferably 20-95 wt%.

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

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 dimethylformamide, methylethylketone, methylisobutylketone 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 0.1 to 100 μm,
Preferably 0.3 to 50 μm, more preferably 0.5 to
30 μm is selected. 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.

The mixing ratio of each component in the primer layer is not particularly limited, but preferably 100 parts by weight of one or more of the above binder polymers, and optionally 0 to 100 parts by weight of a crosslinking agent, It is preferable to add 0 to 100 parts by weight of an additive such as a dye or pigment and 0 to 10 parts by weight of a known catalyst.

In the waterless planographic printing plate of the present invention, the adhesion between the photosensitive layer and the ink repellent layer is very important for basic plate performance such as image reproducibility and printing durability. It is possible to provide an adhesive layer between layers and add an adhesion improving component to each layer. For adhesion between the photosensitive layer and the ink-repellent 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 ink-repellent layer or photosensitive layer. .

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, and are usable for waterless planographic printing plates. Any known ink repellent layer may be used.

When a silicone rubber is used as the ink repellent layer, the silicone rubber layer is usually composed mainly of a linear organic polysiloxane having a repeating unit represented by the following general formula (IX) and a molecular weight of several thousand to several hundred thousand. It is what

[0122]

Embedded image (In the formula, n is an integer of 2 or more, R12 and R13 are carbon atoms 1
~ 50 substituted or unsubstituted alkyl group, carbon number 2
50 substituted or unsubstituted alkenyl groups, having 4 to 4 carbon atoms
It may be at least one selected from the group of 50 substituted or unsubstituted aryl groups and may be the same or different. It is preferable that 40% or less of all R12 and R13 are vinyl, phenyl, vinyl halide and phenyl halide, and 60% or more of all R12 and R13 are methyl groups. Such a linear organic polysiloxane can be made into a further crosslinked silicone rubber by adding an organic peroxide and subjecting it to heat treatment.

The linear organic polysiloxane is usually crosslinked by adding a crosslinking agent represented by the following general formula (X).

R14m SiX4-m (X) (wherein, m is an integer of 0 to 2, R14 represents an alkyl group, an alkenyl group, an aryl group, or a group in which these are combined, and these are a halogen atom, Amine groups,
It may have a functional group such as a hydroxy group, an alkoxy group, an aryloxy group, a (meth) acryloxy group and a thiol group as a substituent. X represents a functional group such as a hydrogen atom, a hydroxyl group alkoxy group, an acyloxy group, a ketoxime group, an amide group, an aminooxy group, an amino group and an alkenyloxy group. As the cross-linking agent, a polyfunctional silane compound used in the above-mentioned so-called room temperature (low temperature) curable silicone rubber can be mentioned. Examples thereof include, but are not limited to, acetoxysilane, ketoximesilane, alkoxysilane, aminosilane, and amidosilane having a trimethoxysilyl group, amino group, glycidyl group, methacryl group, allyl group, vinyl group, and the like.

These are usually combined with linear organic polysiloxanes having a hydroxyl group at the terminal to obtain a deacetic acid type, deoxime type, dealcohol type, deamine type, deamidated type silicone rubber, etc. Become.

Silicone rubbers which are subjected to such condensation type crosslinking include metal carboxylates such as tin, zinc, lead, calcium and manganese, for example dibutyltin laurate, tin (II) octoate and naphthenate. Alternatively, a catalyst such as chloroplatinic acid or a known catalyst other than this may be added.

It is also possible to cure the linear organic polysiloxane with a radical initiator to obtain a silicone rubber. At this time, it is optional to add an appropriate amount of a known radical initiator.

Further, 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, and preferably the following components: (1) Alkenyl group (preferably vinyl group) directly bonded to silicon atom in one molecule. (2) Organopolysiloxane having at least two (2) A composition comprising an organopolysiloxane having at least two SiH bonds in one molecule (3) an addition catalyst, which is crosslinked and cured. Ingredient (1)
The alkenyl group may be at either the terminal or the middle of the molecular chain. Examples of the group other than the alkenyl group include, but are not limited to, a substituted or unsubstituted alkyl group and aryl group. The component (1) may contain a small amount of hydroxyl groups. The component (2) reacts with the component (1) to form a silicone rubber layer, but also 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,
Furthermore, it is preferable that the molecular weight of the component (1) exceeds 1,000.

Examples of the component (1) include α, ω-divinylpolydimethylsiloxane and a (methylsiloxane) (dimethylsiloxane) copolymer having methyl groups at both ends. Examples of the component (2) include hydroxyl groups at both ends. Examples thereof include polydimethylsiloxane, α, ω-dimethylpolymethylhydrogensiloxane, (methylpolymethylhydrogensiloxane) (dimethylsiloxane) copolymer having methyl groups at both ends, and cyclic polymethylhydrogensiloxane. However, the present invention is not limited to this and may be another one.

The addition catalyst of the component (3) is arbitrarily selected from known ones, but a platinum compound is 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 organopolysiloxane such as tetracyclo (methylvinyl) siloxane, carbon-carbon triple bond alcohol, acetone, methylethylketone, methanol,
It is also possible to add an appropriate amount of 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 modulus of elasticity is 0.008 kgf / mm ² or more and 0.1.
Less than 09 kgf / mm ² , preferably 0.012 kgf /
mm ² or more and less than 0.07 kgf / mm ² , and 50% stress value is 0.005 kgf / mm ² or more and 0.04 kgf / mm ²
Less than ² , preferably 0.007 kgf / mm ² or more and 0.0
It is important to make it less than 25 kgf / mm ² .

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 will be poor. On the other hand, the initial elastic modulus is 0.09
kgf / mm ² or more, 50% stress value is 0.04 kgf / mm
^When it is ² or more, for example, the initial tensile elastic modulus of the silicone rubber layer described in Example 1 of JP-B-56-23150 is 0.15 kgf / mm ² , and the 50% stress value is 0.06 kg.
At f / mm ² , since the silicone rubber layer is hard, ink repulsion and scratch resistance are deteriorated.

Further, the elongation of the tensile properties of the silicone rubber layer is 100% or more, preferably 150% or more and 1200%.
It is important to be less than. When the elongation is 100% or less, printing durability becomes poor.

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 resilience, while if it is too thick, it not only is economically disadvantageous, but it also makes it difficult to remove the silicone rubber layer during development, resulting in image reproduction. Cause a decrease in sex.

The blending ratio of each component in the silicone rubber layer is not particularly limited, but in the case of a silicone rubber layer for condensation type crosslinking, the linear organic polysiloxane is 1
00 parts by weight, 0.1 to 100 parts by weight of a silicon compound containing a hydrolyzable functional group directly bonded to a silicon atom, and 0 to 50 parts by weight of a known catalyst may be added if necessary. In the case of the addition type silicone rubber layer, 100 parts by weight of organopolysiloxane having at least two alkenyl groups (preferably vinyl groups) directly bonded to silicon atoms in one molecule, and at least two SiH bonds in one molecule. It is preferable that the organopolysiloxane has 0.1 to 100 parts by weight and, if necessary, an addition catalyst in an amount of 0 to 50 parts by weight.

In the waterless planographic printing plate precursor constructed as described above, in order to protect the ink repellent layer on the surface and to improve the vacuum adhesion of the film in the exposure step, the surface of the ink repellent layer is improved. It is also possible to apply or transfer a laminate or a thin plastic sheet-like thin protective film having a plane or a concavo-convex treatment to form a protective layer. 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 used in the present invention is
For example, it is manufactured as follows. First, a reverse roll roll is placed on a support that has been subjected to various surface roughening treatments as necessary.
, A common coater such as an air knife coater, a maker coater, or a spin coater such as a hoela is used to coat, dry and optionally heat the composition solution for forming the photosensitive layer. Cure. If necessary, a primer layer is provided between the support and the photosensitive layer by the same method as described above, and then an adhesive layer is applied on the photosensitive layer by the same method, if necessary, and dried. , A solution capable of forming an ink repellent layer is applied on the photosensitive layer or the adhesive layer in the same manner, and usually 60-
A wet heat treatment is carried out at a temperature of 130 ° C. for several minutes to sufficiently cure the ink to form an ink repellent layer. If necessary, a protective layer is further applied or a protective film is covered on the ink repellent layer with a laminator or the like. The waterless planographic printing plate produced in this manner is, for example, as it is in the case of a light-transmitting protective film, or is peeled off, and in the case of a film having poor light-transmittance, it is peeled off and then activated through a vacuum-bonded negative film. It is exposed to light rays. The light source used in this exposure step emits a large amount of ultraviolet rays, and a mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, a tungsten lamp, a fluorescent lamp or the like can be used.

Then, if there is a protective film, peel it off and rub the plate surface with a developing pad containing a developing solution to remove the ink repellent layer in the exposed area or, in some cases, the photosensitive layer underneath it. The surface of the primer layer is exposed and becomes an ink receiving portion.

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, but not limited thereto.

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.) Various surfactants such as nonionic surfactants, cationic surfactants and zwitterionic surfactants, and those to which an alkaline agent is added can also be used. As the alkaline agent, for example, sodium carbonate, sodium silicate, sodium hydroxide, potassium hydroxide, an inorganic alkaline agent such as sodium borate, or mono-, di-, or triethanolamine, mono,
Di, or trimethylamine, mono, di, or triethylamine, mono, or diisopropylamine, n-
Examples include organic amine compounds such as butylamine, mono-, di-, or triisopropanolamine, ethyleneimine, and ethylenediimine. Further, a dye such as crystal violet or astrazone red, a color former or the like may be added to the developing solution to dye or color 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. A specific example of the developing device is TW manufactured by Toray Industries, Inc.
Examples thereof include developing devices such as L-1160 and TWL-650, and developing devices disclosed in JP-A-4-2265, JP-A-5-2272, and JP-A-5-6000. Further, these developing devices can be used in an appropriate combination.

[0143]

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. The tensile properties of the photosensitive layer are measured according to JIS K6301. The photosensitive solution was applied onto a glass plate, the solvent was volatilized, and then heat curing was performed at 115 ° C. Then, the sheet was peeled from the glass plate to obtain a sheet having a thickness of about 100 μm. A 5 mm × 40 mm strip-shaped sample was cut out from this sheet, and the initial elastic modulus, 10% stress, and breaking elongation were measured using Tennsilon RTM-100 (manufactured by Orientec Co., Ltd.) at a tensile speed of 20 cm / min. .

The tensile properties of the silicone rubber layer are measured according to JIS
Measure according to K6301. After applying the silicone rubber liquid to the Teflon plate and drying it, peel off the sheet from the Teflon plate, and make a test piece with No. 4 dumbbell from the obtained sheet with a thickness of about 300 microns, Tensilon RT
Using M-100 (manufactured by Orientec Co., Ltd.), the initial elastic modulus, 50% stress, and breaking elongation were measured at a tensile rate of 20 cm / min.

Synthesis Example 1 (Synthesis of quinonediazide compound) Glycidyl acrylyl
47 g and 55 g of 2-hydroxybenzoic acid were dissolved in 200 g of dioxane. Next, 2.7 g of tetraethylammonium bromide and 1.4 g of hydroquinone were added, and the mixture was reacted at 70 ° C. for 4 hours with stirring. After the reaction, the reaction solution was poured into a beaker containing 500 g of water and 500 g of diethyl ether, and the whole solution in this beaker was transferred to a separating funnel. The water layer and the organic layer are separated by a separating funnel, and the solvent of the organic layer is removed by drying under reduced pressure.
A compound having one structure represented by general formula (II) and one structure represented by general formula (III) was obtained.

20 g of this compound and 1,2-naphthoquinone-2-diazide-4-sulfonic acid chloride were dissolved in 100 g of dioxane. Next, sodium carbonate 10G
Is dissolved in 90 g of water, and 10% by weight of this sodium carbonate is added.
The solution was added dropwise to the above dioxane solution over 10 minutes. (At this time, the dioxane solution was stirred and the liquid temperature was kept at 40 ° C.) After completion of the dropping, the reaction was carried out at 40 ° C. for 4 hours with stirring. After the reaction, the reaction solution was poured into a beaker containing 1000 g of water to precipitate and precipitate a product. The supernatant in the beaker was removed and dried under reduced pressure to obtain quinonediazide compound-1.

Synthesis Example 2 (Synthesis of quinonediazide compound) 50 g of the compound obtained in Synthesis Example 1, 5 g of methyl methacrylate and 10 g of hexyl methacrylate were dissolved in 250 g of dioxane, and 0.12 g of azobisisobutyronitrile was added. The polymerization reaction was carried out at 65 ° C. for 4 hours under a nitrogen atmosphere. After the reaction, the reaction solution was poured into a beaker containing 1000 g of methanol,
The product was precipitated and settled. The supernatant in the beaker was removed and dried under reduced pressure to obtain quinonediazide compound-2.

Synthesis Example 3 (Synthesis of quinonediazide compound) Glycerin 50 g and 2
-Hydroxybenzaldehyde 50g, toluene 300
g, 4-benzene sulfonic acid 1 g were mixed, and Dean
-The mixture was heated and refluxed for 5 hours with stirring using a Stark apparatus, and was allowed to react while azeotropically removing water and toluene. When the temperature was returned to room temperature after the reaction, the product and the supernatant (solvent) were separated. The solvent was removed by decantation and dried under reduced pressure to obtain the structure represented by the general formula (II) and the general formula (III
) And the structure shown by each were obtained.

This compound was reacted with 1,2-naphthoquinone-2-diazide-5-sulfonic acid chloride in the same manner as in Synthesis Example 1 to give quinonediazide compound-3.
I got

Synthesis Example 4 (Synthesis of quinonediazide compound) The same reaction as in Synthesis Example 3 was carried out except that 50 g of glycerin was changed to 45 g of trimethylolpropane in Synthesis Example 3 to obtain quinonediazide compound-4. Synthesis Example 5 (Synthesis of silyl group-containing quinonediazide compound) The quinonediazide compound-1 obtained in Synthesis Example 1 was dissolved in dioxane to prepare a 20 wt% solution. To this solution, 15 parts by weight of 3-aminopropyltriethoxysilane was added dropwise with a dropping funnel to 100 parts by weight of the above quinonediazide compound under cooling at 30 ° C., and then reacted for 6 hours to obtain a silyl group-containing compound. The quinonediazide compound-1 was obtained.

Synthesis Example 6 (Synthesis of silyl group-containing quinonediazide compound) The quinonediazide compound-2 obtained in Synthesis Example 2 was dissolved in dry tetrahydrofuran to prepare a 10% by weight solution. To this solution, 30 parts by weight of 3-isocyanatopropyltriethoxysilane was added dropwise at 60 ° C. to 100 parts by weight of the quinonediazide compound under reflux cooling using a dropping funnel. Then, by further reacting for 8 hours, the desired silyl group-containing quinonediazide compound-2 is obtained.
I got

Synthesis Example 7 (Synthesis of silyl group-containing quinonediazide compound) The quinonediazide compound-3 obtained in Synthesis Example 3 was dissolved in dry ethylene glycol dimethyl ether to prepare a 20% by weight solution. To 100 parts by weight of the quinonediazide compound, 20 parts by weight of 3-isocyanatopropyltriethoxysilane was added dropwise to this solution at 60 ° C. under reflux cooling using a dropping funnel. Then, by further reacting for 6 hours, the intended silyl group-containing quinonediazide compound-3 was obtained.

Synthesis Example 8 (Synthesis of silyl group-containing quinonediazide compound) The quinonediazide compound-4 obtained in Synthesis Example 4 was dissolved in tetrahydrofuran to prepare a 20% by weight solution. This solution was added to 100 parts by weight of the above quinonediazide compound,
After adding 0.5 part by weight of dibutyltin diacetate, 30 parts by weight of vinyltri (methylethylketoxime) silane was added dropwise at 40 ° C. to 100 parts by weight of the quinonediazide compound using a dropping funnel. Then, by further reacting for 8 hours, the target silyl group-containing quinonediazide compound-4 was obtained.

Synthesis Example 9 (Synthesis of diazo resin for primer layer) 14.5 g of p-diazodiphenylamine 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 solution was slowly added dropwise so that the temperature did not exceed 10 ° C. Then, stirring was continued under ice cooling for 2 hours. The reaction mixture was added dropwise to 500 ml of ethanol under ice cooling, and the generated precipitate was filtered. The precipitate washed with ethanol is
It was dissolved in 100 ml of water, and a cold concentrated aqueous solution containing 6.8 g of zinc chloride was added to this solution. The resulting precipitate was filtered, washed with ethanol and dissolved in 150 ml of water. To this solution was added a cold concentrated aqueous solution in which 8 g of ammonium hexafluorophosphate was dissolved. The generated precipitate was collected by filtration, washed with water, and dried at 30 ° C. for 24 hours to obtain a diazo resin.

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 “Samprene LQ-T1331” (manufactured by Sanyo Kasei Co., Ltd.) 100 parts by weight (b) Block 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 coated on this primer layer using a bar coater, and the temperature was adjusted to 110 ° C. It was dried in hot air for 1 minute to form a photosensitive layer having a thickness of 1.5 μm.

(A) 70 parts by weight of silyl group-containing quinonediazide compound-1 obtained in Synthesis Example 5 (b) 21 parts by weight of 4,4′-diphenylmethane diisocyanate (c) Polyurethane resin “Miractrane” P22S ( (Manufactured by Nippon Miractolan Co., Ltd.) (glass transition point Tg: -40 ° C) 30 parts by weight (d) dibutyltin diacetate 0.2 parts by weight (e) 4-toluenesulfonic acid 0.8 parts by weight (f) tetrahydrofuran 800 parts by weight Next, a silicone rubber composition having the following composition was spin-coated on this photosensitive layer, and then 115 ° C., dew point 30 ° C., and 3.
It was heat-cured for 5 minutes to form a silicone rubber layer having a thickness of 2 μm.

(A) Polydimethylsiloxane (Molecular weight: about 25,000, terminal hydroxyl group) 100 parts by weight (b) Vinyltri (methylethylketoxime) silane 10 parts by weight (c) "Isopa-E" (manufactured by Exxon Chemical Co., Ltd.) 1,400 parts by weight A 10 μm thick polypropylene film “Trephan” (manufactured by Toray Industries, Inc.) was added to the laminate obtained as described above.
Was laminated with a calendar roller to form a protective layer, and a waterless planographic printing plate precursor was obtained.

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

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 = at room temperature 32 ° C. and humidity 80%. 87 /
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. When 2 (weight ratio) was poured and the plate surface was lightly rubbed with a developing pad, the silicone rubber layer in the image-exposed portion was removed and the surface of the photosensitive layer was exposed, while the non-image portion exposed only to the entire surface was exposed. 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 paper was prepared using "Dry Okara" ink, indigo, red and yellow ink manufactured by Dainippon Ink and Chemicals, Inc. A printing durability test was conducted by printing on.
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 tensile properties of the photosensitive layer used in this example are
As a result of the measurement shown above, the initial elastic modulus is 17 kg.
f / mm @ 2, 10% stress 0.72 kgf / mm @ 2, and breaking elongation 70%.

After the printing plate precursor was prepared,
An image reproducibility was evaluated in the same manner by using a lithographic printing plate precursor after storage for 2 weeks in an atmosphere of relative humidity of 80%.

Example 2 The following primer composition was applied to an aluminum plate having a grain shape on the surface having a thickness of 0.24 mm at 50 ° C. using a whirler and further dried at 80 ° C. for 4 minutes to obtain a primer layer. Was set up.

(A) 8 parts by weight of diazo resin synthesized in Synthesis Example 9 (b) Copolymer resin (Mw = 4.0 × 10 4) (Mw = 4.0 × 10 4) of 2-hydroxyethyl methacrylate and methyl methacrylate in a molar ratio of 40/60 Transition point Tg: −40 ° C.) 90 parts by weight (c) γ-methacryloxypropyltrimethoxysilane (manufactured by Toshiba Silicone) 5 parts by weight (d) Zinc oxide (fine zinc white manufactured by Sakai Chemical Co., Ltd.) 55 parts by weight ( e) “KET-YELLOW 402” (yellow pigment manufactured by Dainippon Ink and Chemicals, Inc.) 12 parts by weight (f) “Nonipol” (nonionic surfactant manufactured by Sanyo Kasei Co., Ltd.) 5 parts by weight (g) Methyl lactate 700 parts by weight (h) Cyclohexanone 100 parts by weight After coating and drying, it is 400 mJ / cm with a metal halide lamp.
2 By exposing and drying at 115 ° C. for 5 minutes, a primer layer having a dry film thickness of 4.5 μm was provided.

Then, the following photosensitive layer composition was applied thereon.
It was applied using a 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) 55 parts by weight of silyl group-containing quinonediazide compound-2 obtained in Synthesis Example 6 (b) 30 parts by weight of trimethylolpropane triglycidyl ether (c) Polyurethane “Samprene” C-800B-40 (Sanyo Kasei Co., Ltd. (Manufactured by Co., Ltd.) (Glass transition point Tg: −35 ° C.) 20 parts by weight (d) Phosphoric acid 0.8 parts by weight (e) 4,4′-Diethylaminobenzophenone 3 parts by weight (f) Tetrahydrofuran 800 parts by weight The silicone rubber composition having the following composition was spin-coated on the photosensitive layer under a stream of dry nitrogen.
C. and dew point of 30.degree. C. were used for 3.5 minutes for wet heat curing to provide a 2.3 .mu.m ink repulsion layer (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) "Isopa -G "(manufactured by Exxon Chemical Co., Ltd.) 1200 parts by weight A single-sided matted polyester film" Lumirror "(manufactured by Toray Industries, Inc.) having a thickness of 8 μm was calendered on the laminated plate obtained as described above. A waterless planographic printing plate precursor was obtained by laminating a protective layer with a laser.

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

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 "Lumira" was peeled off, and 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) 80 parts by weight of diethylene glycol (b) 14 parts by weight of diglycol amine (c) 6 parts by weight of water Further, water was used as a developing solution. A liquid having the following composition was used as the dyeing liquid.

(A) Ethyl carbitol 18 parts by weight (b) Water 79.9 parts by weight (c) Crystal violet 0.1 parts by weight (d) 2-Ethylhexanoic acid 2 parts by weight 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 where only the entire surface was exposed, 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 a printing durability test was conducted in the same manner as in Example 1. 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 tensile properties of the photosensitive layer used in this example are
As a result of measurement by the method shown above, the initial elastic modulus is 16 kg.
f / mm @ 2, 10% stress 0.72 kgf / mm @ 2, and breaking elongation 75%.

Example 3 An aluminum plate having a thickness of 0.24 mm was soaked in a 3% aqueous sodium hydroxide solution to be degreased and washed with water, and then in a 32% aqueous sulfuric acid solution at a temperature of 30 ° C. under conditions of 5 A / dm 2 for 10 seconds.
Anodization was performed, followed by washing with water, immersing in a 2% aqueous sodium metasilicate solution at a temperature of 85 ° C. for 37 seconds, further immersing in water at a temperature of 90 ° C. (pH 8.5) for 25 seconds, washing with water and drying to obtain a support.

The following primer composition was applied to the thus obtained support using a slit die coater and heat-treated for 3 minutes in hot air at 220 ° C. to form a 5 μm primer layer.

(A) Polyurethane resin “Samprene LQ-T1331” (manufactured by Sanyo Chemical Industries, Ltd.) (Glass transition point Tg: −37 ° C.) 100 parts by weight (b) Block 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 -To 0.5 parts by weight (f) Mono (2-methacryloyloxyethyl) acid phosphate 1 part by weight (g) Dimethylformamide 700 parts by weight (h) Tetrahydrofuran 50 parts by weight Then, the following composition was formed on the primer layer. Immediately before coating, the photosensitive liquid (A) and the photosensitive liquid (B) are applied, coated using a slit die coater, and dried in hot air at 115 ° C for 1 minute. And a photosensitive layer having a thickness of 1.5μm by.

Photosensitive Solution (A) (a) 80 parts by weight of silyl group-containing quinonediazide compound-2 obtained in Synthesis Example 6 (b) Polyurethane "Samprene" C-800B-40 (manufactured by Sanyo Chemical Industry Co., Ltd.) ( Glass transition point Tg: -35 ° C) 20 parts by weight (c) Dibutyltin diacetate 0.2 parts by weight (d) Benzenesulfonic 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 Next, a silicone rubber liquid having the following composition was applied onto the photosensitive layer using a slit die coater, and then 12
It was heat-cured at 0 ° C. for 4 minutes to provide an ink-repellent layer (silicone rubber layer) having a thickness of 1.8 μm.

(A) Polydimethylsiloxane having 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 up to 8000) ) 10 parts by weight (f) "ISOPA-E" (manufactured by Exxon Chemical Co., Ltd.) 1000 parts by weight The laminated plate obtained as described above is coated with a polyester film "Lumirror" (manufactured by Toray Industries, Inc.) having a thickness of 8 μm. Was laminated with a calendar roller to form a protective layer to obtain a waterless planographic printing plate precursor.

After subjecting the printing plate precursor to the same treatment as in Example 2, image exposure was carried out using a negative film having a halftone dot image of 150 lines / inch, and development was carried out 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 it showed a printing durability of 160,000 sheets.

The tensile properties of the photosensitive layer used in this example are
As a result of measurement by the method shown above, the initial elastic modulus is 16 kg.
f / mm @ 2, 10% stress 0.74 kgf / mm @ 2, and breaking elongation 76%.

Example 4 Example 1 was repeated except that the photosensitive layer component (a) silyl group-containing quinonediazide compound-1 in Example 1 was replaced with (a) silyl group-containing quinonediazide compound-3 obtained in Synthesis Example 7. Similarly, a waterless planographic printing plate precursor was prepared.
The obtained waterless planographic printing plate precursor was exposed, developed and printed in the same manner as in Example 2. Table 2 shows the evaluation results of plate performance.
Shown in

Example 5 Example 3 was repeated except that the photosensitive layer component (a) silyl group-containing quinonediazide compound-2 in Example 3 was replaced with (a) silyl group-containing quinonediazide compound-4 obtained in Synthesis Example 8. Similarly, a waterless planographic printing plate precursor was prepared.
The obtained waterless planographic printing plate precursor was exposed, developed and printed in the same manner as in Example 3. Table 2 shows the evaluation results of plate performance.
Shown in

Comparative Examples 1 to 4 photosensitive layer component (a) silyl group-containing quinonediazide compound-1 in Example 1, photosensitive layer component (a) silyl group-containing quinonediazide compound-2 in Example 3 and photosensitive layer in Example 4 Component (a) silyl group-containing quinonediazide compound-3 and photosensitive layer component (a) silyl group-containing quinonediazide compound-4 in Example 5 were respectively (a) quinonediazide compound-obtained in Synthesis Example 1-
1, (a) quinonediazide compound obtained in Synthesis Example 2
2, (a) quinonediazide compound obtained in Synthesis Example 3
3, (a) quinonediazide compound obtained in Synthesis Example 4
A waterless planographic printing plate precursor was prepared in the same manner as in each of the examples except that the substituting method was changed to 4. The obtained waterless planographic printing plate precursor was exposed, developed and printed in the same manner as in Example 3 to evaluate plate performance. Table 2 shows the results.

Examples 6 to 8 Plates were prepared in the same manner as in Example 4 except that the photosensitive layer component (a) in Example 4 was changed as shown in Table 1. Example 4
Similarly, the plate performance was evaluated. Table 2 shows the results. Examples 9 to 17 Various binder polymers 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 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 4 shows the tensile properties of the photosensitive layer and the image reproducibility and printing durability of the printing plate.

[0190]

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

[0191]

Since the present invention is constructed as described above,
A waterless lithographic printing plate excellent in image reproducibility, printing durability and storage stability can be provided.

Therefore, it can be suitably used also in the field of newspaper off-wheel printing and the field of commercial off-wheel printing where high printing durability is required.

Claims (10)

[Claims] 1. A waterless planographic printing plate precursor comprising at least a photosensitive layer and a silicone rubber layer laminated in this order on a support, wherein the photosensitive layer has at least one structure represented by the following general formula (I). A waterless planographic printing plate containing at least one structure represented by the following general formula (II) and at least one quinonediazide compound having at least one structure represented by the following general formula (III) Original printing plate. —SiR _n X _3-n (I) (In the formula, n is an integer of 0 to 3, R represents an alkyl group, an alkenyl group, an aryl group, or a group in which these are combined, and they are a halogen atom, It may have a functional group such as an isocyanate group, an epoxy group, an amino group, a hydroxy group, an alkoxy group, an aryloxy group, a (meth) acryloxy group and a mercapto group as a substituent.
Indicates a functional group. ) -R1-OH (II) -Ph (R2) (R3) (R4) (R5) (OH) (III) (In the formula, R1 is a sulfur atom, a substituted or unsubstituted nitrogen atom, a substituted or unsubstituted nitrogen atom, It is at least one selected from the group of carbon atoms and substituted or unsubstituted silicon atoms, Ph is an aromatic ring, and R2, R3, R4, and R5 are substituents, which may be the same or different. ^2. The waterless planographic printing plate precursor as claimed in claim 1, wherein the tensile properties of the photosensitive layer after exposure have the following physical properties: (1) initial elastic modulus: 5 to 50 kgf / mm ² . 3. The waterless planographic printing according to claim 1, wherein the tensile properties of the photosensitive layer after exposure have the following physical properties: (2) 10% stress: 0.05 to 3.0 kgf / mm ^2. Original edition. 4. The waterless lithographic printing plate precursor as claimed in claim 1, wherein the photosensitive layer has physical properties of (3) elongation at break: 10% or more after exposure. 5. The waterless lithographic printing plate precursor according to claim 1, wherein the photosensitive layer contains a binder polymer. 6. A waterless planographic printing plate precursor according to claim 5, wherein the proportion of the binder polymer in the photosensitive layer is 10 to 90 wt%. 7. The waterless lithographic printing plate precursor as claimed in claim 5, wherein the binder polymer has a glass transition point (Tg) of 20 ° C. or lower. 8. The waterless planographic printing plate precursor as claimed in claim 1, wherein the photosensitive layer has a crosslinked structure. 9. The waterless lithographic printing plate precursor according to claim 1, wherein the photosensitive layer is a photo-peeling photosensitive layer. 10. A waterless lithographic printing plate obtained by selectively exposing and developing the waterless lithographic printing plate precursor according to claim 1.