JPH09197658A - Waterless planar printing plate master - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make up the polymerizing efficiency of a photo-polymerization type photo-sensitive layer for its drawback such that the polymerizing efficiency is low at a low temperature, and the adhesion of a photo-dimerization type photo-sensitive layer for its drawback such that the adhesion thereof is low with respect to an ink repulsive layer. SOLUTION: In a waterless planer printing plate master in which a photo-sensitive layer and an ink-repulsive layer are successively stacked on a substrate, the photo-sensitive layer contains both at least one photo-dimerizable reaction group and at least one of photo-polymerizable reaction group or contains both compound having at least one photo-dimerizable reaction group and compound having at least one photo-polymerizable reaction group.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a waterless lithographic printing plate precursor capable of printing without using a fountain solution, and particularly to a waterless lithographic printing plate excellent in image reproducibility, solvent resistance and printing durability. It relates to a lithographic printing plate.

[0002]

2. Description of the Related Art Various waterless lithographic printing plates have been proposed for lithographic printing without using fountain solution. Above all, 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 proposed in Japanese Patent Publication No. 54-26923 or Japanese Patent Publication No. 56-23150, Japanese Patent Fair 3-566
No. 22 and JP-A-61-153655, a waterless planographic 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, and JP-B-61- JP-A-61-54222, or a waterless planographic printing plate having a silicone rubber layer, which is an ink repellent layer, provided on a photosensitive layer containing a support-backed orthoquinonediazide compound, which is proposed in Japanese Patent No. 54218, via an adhesive layer. A waterless lithographic printing plate, which has a silicone rubber layer as an ink repellent layer provided on a light-releasing photosensitive layer proposed in Japanese Patent Publication, can be printed practically without using fountain solution.

Among these, a photopolymerizable adhesive layer and a silicone rubber layer as an ink repellent layer are laminated on a substrate proposed in Japanese Patent Publication No. 54-26923 or Japanese Patent Publication No. 56-23150. In waterless lithographic printing plates, the low polymerization efficiency at low temperatures reduces the adhesive force between the photosensitive layer and the silicone rubber layer, which is the ink repellent layer, in cold regions and in winter, causing the silicone rubber layer to fall off and high resistance. The printability was not obtained.

Further, in the waterless planographic printing plate using the photodimerization type photosensitive layer described in JP-A-3-56622 and JP-A-61-153655, a silicone rubber which is a photosensitive layer and an ink repellent layer is used. Since the adhesive strength with the layer was small, the silicone rubber layer fell off and high printing durability could not be obtained.

Further, in the waterless lithographic printing plate using the photodegradable photosensitive layer described in JP-B-61-54218 and JP-B-61-54222, the photosensitive layer is destroyed and the ink repellent layer is generated. It has been found that even a certain silicone rubber layer is cracked and high printing durability cannot be obtained.

From the viewpoint of image reproducibility, Japanese Patent Laid-Open No. 5-281
No. 714 and JP-A No. 6-67411, a diamine compound at both terminals is reacted with glycidyl (meth) acrylate to improve the sensitivity of the printing plate. However, although this method surely increases the sensitivity, in the above printing durability test results, it was found that high printing durability cannot be obtained due to breakage at the adhesive interface between the photosensitive layer and the silicone rubber layer, which is the ink repellent layer. I understood.

[0007]

Therefore, the object of the present invention is to provide a photosensitive layer containing a compound having at least one photodimerizable reactive group and at least one photopolymerizable reactive group. It is possible to compensate for the low polymerization efficiency at low temperature, which is a drawback of the photopolymerization type photosensitive layer, and to compensate for the low adhesive strength between the photosensitive layer and the ink repellent layer, which is the drawback of the conventional photodimerization type photosensitive layer. Provides a waterless lithographic printing plate precursor that is excellent in image reproducibility and printing durability, and is also excellent in solvent resistance because the entire photosensitive layer after exposure is not as hard and brittle as the photopolymerizable photosensitive layer. Especially.

[0008]

The present invention is achieved by the following waterless lithographic printing plate.

(1) In a waterless lithographic printing plate precursor in which a photosensitive layer and an ink repellent layer are sequentially laminated on a support, the photosensitive layer has at least 1 of both photodimerizable and photopolymerizable reactive groups. A waterless lithographic printing plate precursor comprising a compound having each of them.

(2) In a waterless planographic printing plate precursor in which a photosensitive layer and an ink repellent layer are sequentially laminated on a support, the photosensitive layer is photopolymerizable with a compound having at least one photodimerizable reactive group. A waterless lithographic printing plate precursor comprising at least one compound having at least one group.

(3) The waterless lithographic printing plate precursor as described in (1) or (2), wherein the photodimerizable reactive group is a photodimerable unsaturated double bond.

(4) The photopolymerizable reactive group is a photopolymerizable unsaturated double bond (1) to (1)
The waterless planographic printing plate precursor as described in any of (3).

(5) The waterless lithographic printing plate precursor as described in any of (1) to (4), wherein the photodimerizable reactive group is represented by the following general formula (I).

[0014]

Embedded image (In the formula, R1 to R4 are each independently a hydrogen atom, an amino group, a nitro group, a hydroxyl group, a mercapto group, a halogen atom,
A substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, an alkoxy group, a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms, an alkenyloxy group, a substituted or unsubstituted aryl group having 4 to 50 carbon atoms, aryl At least one selected from the group of oxy groups, an ether bond, an ester bond, a carbonate bond, a urethane bond, in the chain,
It may contain at least one selected from the group consisting of a urea bond, an amide bond, a thioether bond, an amino bond and a carbonyl bond. R5 and R6 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, an alkoxy group, a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms, an alkenyloxy group, or 4 to 4 carbon atoms.
It is at least one selected from the group of 50 substituted or unsubstituted aryl groups and aryloxy groups, and has an ether bond, an ester bond, a carbonate bond, a urethane bond, a urea bond, an amide bond, a thioether bond, an amino bond, in the chain. It may contain at least one selected from the group of carbonyl bonds. (6) The compound having a photodimerizable reactive group is a polymer compound having a structure represented by the general formula (I) in a main chain or a side chain and having a molecular weight of 500 to 5,000,000. A waterless planographic printing plate precursor as described in any of (1) to (5) above.

(7) The waterless planographic printing plate precursor as described in any one of (1) to (6), wherein the ink repellent layer has a photodimerizable reactive group.

(8) The photo-dimerizable reactive group of the ink repellent layer is represented by the following general formula (II) (7)
The waterless planographic printing plate precursor described.

[0017]

Embedded image (In the formula, R1 to R6 are independently the same as in the general formula (I).) (9) The ink repulsion layer is a silicone rubber layer crosslinked by a condensation reaction between a SiOH group and a hydrolyzable crosslinking agent. A waterless planographic printing plate precursor as described in any one of (1) to (8), characterized in that

(10) The ink repellent layer contains SiH groups and --CH.
A waterless planographic printing plate precursor as described in any one of (1) to (8), which is a silicone rubber layer crosslinked by an addition reaction with a = CH- group.

(11) A waterless lithographic printing plate obtained by selectively exposing and developing the waterless lithographic printing plate precursor as described in any one of (1) to (10).

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION The constitution of the present invention will be described more specifically below.

As the support of the lithographic printing plate used in the present invention, a dimensionally stable plate is used. Examples of such a dimensionally stable plate-like material include those conventionally used as a support for a printing plate, and they can be preferably used. Examples of such a support include paper, paper laminated with plastic (eg, polyethylene, polypropylene, polystyrene, etc.), metal plate such as aluminum (including aluminum alloy) zinc, copper, etc. Cellulose acetate,
Films of plastics such as cellulose propionate, cellulose acetate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc., papers or plastic films laminated or vapor-deposited with the above metals. Is included. Among these supports, the aluminum plate is particularly preferable because it is extremely stable in dimension and inexpensive. Further, a composite sheet in which an aluminum sheet is bonded onto polyethylene terephthalate as described in JP-B-48-18327 is also preferable.

The waterless planographic printing plate precursor used in the present invention may be provided with a primer layer in order to strengthen the adhesion between the support and the photosensitive layer. The primer layer of the waterless planographic printing plate precursor used in the present invention needs to satisfy the following conditions. That is, it is that the support and the photosensitive layer are well adhered to each other, stable over time, and that the solvent resistance of the developer to the solvent is good. As those satisfying such conditions, in addition to those containing an epoxy resin as shown in Japanese Patent Publication No. 61-54219, urethane resin, phenol resin, acrylic resin, alkyd resin, polyester resin, polyamide resin, melamine resin, urea Resins, benzoguanamine resins, vinyl chloride-vinyl acetate copolymers, vinyl chloride resins, polyvinyl butyral resins, ethylene-vinyl acetate polymers, polycarbonate polymers, milk casein, gelatin and the like can be used. These resins may be used alone or in combination of two or more.

A composition obtained by photocuring a composition similar to the photosensitive layer may be used.

It is also optional to add a surfactant for the purpose of improving the coatability.

Further, these primer layers may contain additives such as dyes and pigments for the purpose of preventing halation and other purposes.

The thickness of the primer layer is 0.5 to 0.5 as a coating layer.
50 g / m @ 2 is preferred, more preferably 1-10 g / m @ 2
m2.

The photosensitive layer used in the present invention contains at least one photo-dimerizable reactive group and at least one photo-polymerizable reactive group.
The greatest feature is that it contains compounds having each of them. Alternatively, a compound having at least one photodimerizable reactive group and at least one photopolymerizable reactive group
The greatest feature is that it contains at least one of each of the two compounds.

The advantage of the photodimerizable reactive group is that the temperature dependence is small, and conversely, the drawback is that the reactivity is smaller than that of photopolymerization. On the other hand, the advantage of the photopolymerizable reactive group is that the reactivity is higher than that of the photodimerization, and conversely, the temperature dependency is large as a drawback. Therefore, if it has both a compound having both a photodimerizable reactive group and a photopolymerizable reactive group, or a compound having a photodimerizable reactive group and a compound having a photopolymerizable reactive group, It is possible to make the most of each advantage and compensate for each drawback. For example, when exposed at a low temperature, the insufficient photopolymerization of the photopolymerizable reactive group can be compensated by the photodimerizable reactive group. When the exposure time is short or the exposure amount is small, the insufficient reaction of the photodimerizable reactive group can be compensated by the photopolymerizable reactive group. For this reason, the photosensitive layer of the present invention undergoes a complete curing reaction upon exposure, so the photosensitive layer after exposure becomes insoluble in a solvent and therefore has excellent solvent resistance, and the difference between the exposed and unexposed areas is high. Is remarkable, so that the difference can be clearly drawn out by the development, so that the image reproducibility is excellent, and the adhesion between the photosensitive layer and the ink repellent layer is naturally improved, so that the printing durability can be excellent.

The reactive group capable of photodimerization is not particularly limited, but those having a structure represented by the following general formula (I) are preferably used.

[0030]

Embedded image (In the formula, R1 to R4 are each independently a hydrogen atom, an amino group, a nitro group, a hydroxyl group, a mercapto group, a halogen atom,
A substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, an alkoxy group, a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms, an alkenyloxy group, a substituted or unsubstituted aryl group having 4 to 50 carbon atoms, aryl At least one selected from the group of oxy groups, an ether bond, an ester bond, a carbonate bond, a urethane bond, in the chain,
It may contain at least one selected from the group consisting of a urea bond, an amide bond, a thioether bond, an amino bond and a carbonyl bond. R5 and R6 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, an alkoxy group, a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms, an alkenyloxy group, or 4 to 4 carbon atoms.
It is at least one selected from the group of 50 substituted or unsubstituted aryl groups and aryloxy groups, and has an ether bond, an ester bond, a carbonate bond, a urethane bond, a urea bond, an amide bond, a thioether bond, an amino bond, in the chain. It may contain at least one selected from the group of carbonyl bonds. The following are specific examples of the structure represented by formula (I), but the structure is not limited thereto.

[0031]

[Chemical 6] Examples of the compound having at least one photodimerizable reactive group and at least one photopolymerizable reactive group include, for example, U.S. Pat. No. 3,030,208 and 3,707,373.
Photosensitive polyesters derived from a photopolymerizable reactive group-introduced compound, a cinnamylidene malonic acid compound and polyfunctional glycols as described in Japanese Patent No. 3453237 (for example, US Patent No. 29568).
No. 78, No. 3173787, a photosensitive polymer as a main component and further introduced with a photopolymerizable reactive group, a hydroxyl group such as polyvinyl alcohol, starch, cellulose and the like. Cinnamate esters of polymers containing (US Pat. No. 2,690,301)
(Polymers described in JP-B Nos. 2752372 and 2732301) into which a photopolymerizable reactive group is introduced, JP-A-58-25302 and JP-A-59-17550. Examples thereof include those obtained by introducing a photopolymerizable reactive group into the described polymer.

Further, it is not necessary that the compound has a high molecular weight as described above, and a compound containing both a cinnamoyl structure and an unsaturated double bond, a compound containing both a cinnamoyl structure and an epoxy structure, etc. are effective. . For example, an esterification product of cinnamic acid and hydroxyethyl acrylate, an esterification product of cinnamic acid and hydroxyethyl methacrylate, a reaction product of cinnamic acid and glycidyl acrylate, a reaction product of cinnamic acid and glycidyl methacrylate, cinnamic acid With epichlorohydrin, cinnamyl aldehyde and ethanolamine with an acrylic or methacrylic group introduced, an esterified product of cinamyl alcohol and acrylic acid, cinamyl alcohol and methacrylic acid But not limited thereto, a compound having at least one photodimerizable reactive group and at least one photopolymerizable reactive group. Anything will do as long as it is. In particular, as the photodimerizable reactive group, a cyclohexene structure, a norbornene structure, an anthracene structure, or the like is effective, and a group other than these may be used.

Examples of the photopolymerizable reactive group include an ethylenically unsaturated bond and an epoxy structure. When an ethylenically unsaturated bond is introduced, radical polymerization proceeds,
When the epoxy structure is introduced, the polymerization proceeds cationically.

The amount of the compound having at least one photo-dimerizable reactive group and at least one photo-polymerizable reactive group is preferably 5 to 95% by weight with respect to the total photosensitive layer composition, and more preferably. It is 10 to 90% by weight. When the amount used is less than 5% by weight, the image reproducibility of the plate decreases, and when it is more than 95% by weight, the storage stability of the plate decreases.

In addition to the above components, it is possible to add other polymerizable monomers or oligomers for the purpose of controlling image reproducibility. Examples of such polymerizable monomers include known amine-based monomers and non-amine-based monomers. In particular, from the viewpoint of adhesion to the upper ink repellent layer, an amine monomer containing a hydroxyl group or a non-amine monomer is preferable, but not limited thereto.

Specific examples of amine-based monomers include those obtained by reacting an amine compound with glycidyl methacrylate or methacrylic acid. Specific examples of the amine compound, methylamine, butylamine, hexylamine, aniline, ethylenediamine, hexamethylenediamine, xylylenediamine, trioxyethylenediamine, tetraoxyethylenediamine, polyoxyethylenediamine, trioxypropylenediamine, tetraoxypropylenediamine, Examples thereof include polyoxypropylene diamine. In this case, it is not necessary to react a compound having an ethylenically unsaturated bond with all amino groups, and it is optional to partially react with methyl glycidyl ether, butyl glycidyl ether, acetic acid, propionic acid or the like. When glycidyl methacrylate is reacted, these are compounds having at least one amino group structure and at least one ethylenically unsaturated bond, and at least one hydroxyl group. When methacrylic acid is reacted, the compound has at least one amino group structure and at least one ethylenically unsaturated bond. Further, the compound is not limited to the above amine-based monomer, and any compound may be used as long as it has at least one amino group structure and at least one photopolymerizable reactive group.

Specific examples of the non-amine type monomer include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate, and polyethylene glycol di ( (Meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane Tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, calcium (meth) acrylate, (meth) ac Sodium le acid, after adding ethylene oxide or propylene oxide to a polyfunctional alcohol such as glycerin or trimethylolethane (meth) those acrylated, JP-B-48-41
No. 708, JP-B-48-64183, JP-B-49-43191 and JP-B-52-3-490, polyester acrylates, epoxy resins and (meth) acrylic acid were reacted. Examples thereof include polyfunctional acrylates and methacrylates such as epoxy acrylates. These are compounds having no amino group structure and having at least one photopolymerizable reactive group, and some of the compounds further have at least one hydroxyl group.

The amount of these polymerizable monomers or oligomers used is preferably 20 to 80% by weight, more preferably 30 to 70% by weight, based on the total photosensitive layer composition, but the features of the present invention are maximized. In order to make the best use of it, it is preferable to use it in an amount smaller than that of a compound having at least one photodimerizable reactive group and at least one photopolymerizable reactive group.

In addition, a compound having at least one photodimerizable reactive group and at least one photopolymerizable reactive group
In the case of containing at least one of both compounds each having one, specific examples of the compound having at least one photodimerizable reactive group are described in US Pat. No. 3,030,208, No. 3,707,373, and No. 3,453,237. Photosensitive polyesters derived from compounds such as those described, cinnamylidene malonic acid compounds and polyfunctional glycols (eg, photopolymerizable polyesters such as those described in US Pat. Nos. 2,956,878 and 3,173,787). Cinnamic acid esters of hydroxyl group-containing polymers such as polyvinyl alcohol, starch, cellulose and the like (US Pat.
No. 690301, No. 2752372, No. 27
No. 32301)
Examples thereof include the polymers described in JP-A-8-25302 and JP-A-59-17550. Further, it is not necessary for the compound to have a high molecular weight as described above, and a compound containing a cinnamoyl structure, a cyclohexene structure, a norbornene structure, an anthracene structure, or the like is also effective, and other compounds may be used.

Of these, from the viewpoint of improving the efficiency of photoreactivity, it is preferable to use two or more compounds in appropriate amounts in combination, and a compound having two or more photodimerizable reactive groups is more preferable. It is most preferable to have a hydroxyl group or an ethylenically unsaturated bond capable of adhering to the upper ink repellent layer.

Further, at least one photopolymerizable reactive group is included.
Examples of the compound having one are the amine-based monomers and the non-amine-based monomers described above, but other compounds may be used. Among these, it is preferable to have two or more photopolymerizable reactive groups, it is more preferable to use two or more kinds of compounds in appropriate amounts in combination, and it is preferable to use a hydroxyl group or a hydroxyl group capable of adhering to the upper ink repulsion layer. Most preferably, it has an ethylenically unsaturated bond.

The mixing ratio of the compound having at least one photodimerizable reactive group and the compound having at least one photopolymerizable reactive group is not particularly limited, but the ratio of the compound having a photopolymerizable reactive group is 5 It is preferably ˜95%. When the amount of the compound having a photopolymerizable reactive group is extremely small, the photoreactivity of the entire photosensitive layer is lowered and the solvent resistance to a pretreatment liquid, a developing liquid and a posttreatment liquid described later is lowered.
Further, when the amount of the compound having a photopolymerizable reactive group is extremely large, the photoreactivity at low temperature which is the maximum effect of the present invention is lowered, so this range is preferable.

At least one reactive group capable of photodimerization is used.
The amount of the mixture of the compound having one photopolymerizable compound and the compound having at least one photopolymerizable reactive group is preferably 5 to 95% by weight, more preferably 10% by weight, based on the total photosensitive layer composition.
~ 90% by weight. When the amount used is less than 5% by weight, the image reproducibility of the plate decreases, and when it is more than 95% by weight, the storage stability of the plate decreases.

In the light-sensitive layer of the waterless lithographic printing plate of the present invention, it is also preferable to add an appropriate amount of a polymer compound having a film-forming ability from the viewpoint of shape retention and the like.
Examples of such polymer compounds include methacrylic acid copolymers, acrylic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, acidic cellulose derivatives, polyvinylpyrrolidone, polyethylene. Oxide, alcohol-soluble nylon, polyester, unsaturated polyester, polyurethane, polystyrene, epoxy resin, phenoxy resin, polyvinyl butyral, polyvinyl formal, polyvinyl chloride, polyvinyl alcohol, partially acetalized polyvinyl alcohol, water-soluble nylon, water-soluble urethane resin, gelatin,
Examples thereof include water-soluble cellulose derivatives.

These high molecular compounds capable of forming a film can be used alone or in combination of two or more. The amount of the polymer compound having film-forming ability to be used is preferably 10 to 90% by weight, more preferably 30 to 70% by weight, based on the total photosensitive layer composition. When the amount used is less than 10% by weight, the printing durability of the photosensitive layer is lowered, and when it is more than 90% by weight, the developability tends to be lowered.

Further, since the photosensitive layer of the waterless lithographic printing plate of the present invention causes a photoreaction, it is preferable to add an appropriate photoinitiator or photosensitizer. Examples of such photopolymerization initiators and photosensitizers include vicinal polyketaldonyl compounds disclosed in US Pat. No. 2,367,660, and α-carbonyl compounds disclosed in US Pat. Nos. 2,367,661 and 2,367,670. U.S. Pat. No. 248
8828 gazette, an acyloin ether disclosed in U.S. Pat. No. 2,722,512, and an aromatic acyloin compound having an .alpha.-position substituted with a hydrocarbon, shown in U.S. Pat. No. 2,722,512, U.S. Pat. No. 29.
No. 51758, a polynuclear quinone compound, a combination of a triarylimidazole dimer / p-aminophenyl ketone shown in US Pat. No. 3,549,367, a benzothiazole compound shown in US Pat. No. 3,870,524, and a US Pat. No. 4,239,850. Benzothiazole compound / trihalomethyl-s-triazine compound disclosed in U.S. Pat.
59, acridine and phenazine compounds, U.S. Pat. No. 4,212,970, oxadiazole compounds, U.S. Pat. No. 3,954,475, JP-A-53-133428, U.S. Pat. No. 4,189.
323, JP-A-60-105667, JP-A-63-153542, and trihalomethyl-s-triazine compounds having a chromophore group, JP-A-5.
Examples thereof include benzophenone group-containing belloxy ester compounds disclosed in JP-A No. 9-197401 and JP-A No. 60-76503. Photoacid generators such as benzoin tosylate and various onium salt compounds are also effective as photoinitiators. The amount of these photopolymerization initiators added is preferably 0.1 to 20% by weight, more preferably 1 to 15% by weight, based on the total photosensitive layer composition. When it is less than 0.1% by weight, the image reproducibility is lowered, and when it is more than 20% by weight, the developability is lowered.

In addition to the above, a small amount of a photocurable diazo resin may be added to the photosensitive layer in order to improve the adhesion with the primer layer. Examples of such diazo resins include US Pat. No. 3,867,147 and US Pat. No. 263270.
Examples thereof include those described in JP-A No. 3, but a diazo resin represented by a condensate of an aromatic diazonium salt and an active carbonyl-containing compound (eg formaldehyde) is particularly useful. Preferred diazo resins include, for example, hexafluorophosphate, tetrafluoroborate, and phosphate of a condensate of p-diazodiphenylamine and formaldehyde or acetaldehyde. Also, US Pat.
Sulfonates of the condensates of p-diazodiphenylamine and formaldehyde as described in JP 00309 (eg p-toluene sulfonate, dodecylbenzene sulfonate, 2-methoxy-4-hydroxy-5-benzoyl). Benzene sulfonate, etc.), phosphinate, organic carboxylate, etc. are also preferable. The preferable addition amount of the above diazo resin is 0.
It is 1 to 5% by weight.

Further, it is preferable to add a thermal polymerization inhibitor to the photosensitive layer. For example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone,
4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-)
t-butylphenol), 2-mercaptobenzimidazole and the like are useful.

In some cases, a dye or pigment, a pH indicator as a printout agent, or a leuco dye may be added for the purpose of coloring the photosensitive layer. Depending on the purpose, a small amount of polydimethylsiloxane, methylstyrene-modified polydimethylsiloxane, olefin-modified polydimethylsiloxane, polyether-modified polydimethylsiloxane, silane coupling agent, silicone diacrylate, silicone dimethacrylate, or other silicone compound in the photosensitive layer, depending on the purpose. May be added. Further, a fluorine-containing surfactant may be added to improve the suitability for coating. The amount of these additives is usually 10% by weight or less based on the total photosensitive layer composition.

In some cases, silica powder or hydrophobic silica powder whose surface is treated with a silane coupling agent containing a (meth) acryloyl group or an allyl group is used for the entire photosensitive layer in order to enhance the adhesion to the ink repellent layer. 50 for composition
You may add in the quantity of less than weight%.

In the present invention, the initial elastic modulus of the photosensitive layer after exposure is 5 to 75 kgf / mm 2, preferably 10 to 65 kgf / mm 2, and more preferably 10 to 60 kgf / mm 2.
kgf / mm2, more preferably 10 to 50 kgf /
mm2. Initial elastic modulus after exposure is 5kgf / mm2
If it is less than the range, the photosensitive layer becomes brittle and the photosensitive layer is destroyed during printing. If it exceeds 75 kgf / mm2, the photosensitive layer becomes hard, and when offset printing is performed, repeated stress is applied between the photosensitive layer and the ink repellent layer, causing breakage at the adhesive interface between the photosensitive layer and the ink repellent layer. Printing durability cannot be obtained.

Furthermore, the elongation at break of the photosensitive layer after exposure is 10
It is preferably 0% or more. More preferably 120
% Or more, more preferably 150% or more. When the breaking elongation is less than 100%, the photosensitive layer becomes brittle, and when offset printing is performed, the photosensitive layer is broken and high printing durability cannot be obtained.

Further, the 50% stress value after exposure of the photosensitive layer is preferably 0.5 to 3.8 kgf / mm 2. It is more preferably 1.0 to 3.2 kgf / mm @ 2, and even more preferably 1.2 to 2.6 kgf / mm @ 2.
If the 50% stress value is less than 0.5 kgf / mm @ 2, the photosensitive layer becomes sticky and becomes a cause of hickiness during printing. 3.8
If it exceeds kgf / mm2, the repeated stress due to the hardness of the photosensitive layer, that is, the repeated stress is applied between the photosensitive layer and the ink repellent layer, and the adhesive interface between the photosensitive layer and the ink repellent layer is broken. Occurs, and high printing durability cannot be obtained.

Here, the initial elastic modulus after exposure of the photosensitive layer, the elongation at break, and the 50% stress value are those measured by the following methods.

[Initial elastic modulus of the photosensitive layer, elongation at break, 50%
Method of Measuring Stress Value] The tensile properties of these photosensitive layers are determined by JI
It can be measured according to SK6301. That is, the unexposed waterless planographic printing plate precursor is dipped in a soluble solvent to be dropped and dissolved from the substrate of the silicone rubber layer and the photosensitive layer. The obtained solution is filtered to separate the unnecessary silicone rubber layer in the soluble solvent. Furthermore, the liquid is solid content 30%
Concentrate under reduced pressure to obtain a photosensitive solution. The photosensitive solution was applied to a glass plate, dried, and then the sheet was peeled off from the glass plate, and a test piece was prepared from the obtained sheet having a thickness of about 300 μm with a No. 4 dumbbell, and a 3 kW ultra-high pressure mercury lamp (Oak Seisakusho). ) Using a UV meter (Oak Seisakusho Light Measure Type UV365) at an illuminance of 12 mW / cm2.
After exposure for 0 minutes, Tensilon RTM-100 (manufactured by Orientec Co., Ltd.) was used at a tensile speed of 20 cm / min to obtain J
Initial elastic modulus, elongation at break, 50 according to IS K6301
The% stress value is measured.

The thickness of the photosensitive layer is 0.2 to 20 as a coating layer.
g / m @ 2 is preferred, more preferably 0.5-10 g
/ M2.

Examples of the ink repellent layer used in the present invention include silicone rubber and fluorine-containing compounds (for example, rubber having fluorine in the molecule). Silicone rubber is preferably used because of easy material supply.
The silicone rubber layer needs to be transparent to ultraviolet rays. Such a silicone rubber layer is obtained by sparsely cross-linking a linear organopolysiloxane (preferably dimethylpolysiloxane), and a typical silicone rubber layer is represented by the following formula (III). It has a repeating unit.

[0058]

Embedded image (In the formula, n is an integer of 2 or more. R8 and R9 are each independently a substituted or unsubstituted alkyl, alkenyl, aryl, or cyanoalkyl group having 1 to 10 carbon atoms. 40% or less is vinyl, phenyl, vinyl halide, phenyl halide,
It is preferable that 60% or more of R8 and R9 are methyl groups. Further, it has at least one or more hydroxyl group in the molecular chain at the chain end or in the form of a side chain. In the case of the silicone rubber layer applied to the printing plate of the present invention, a silicone rubber (R
TV, LTV type silicone rubber) is used. As such a silicone rubber, R of an organopolysiloxane chain is used.
Although a compound in which a part of 8 and R9 is replaced by a hydrogen atom can also be used, it is usually crosslinked by condensation of terminal groups represented by the following formulas (IV) and (V) and (VI). In some cases, an excess of a crosslinking agent may be present. Such silicone rubber may contain a photodimerizable reactive group (for example, as used in the above-mentioned photosensitive layer).

[0059]

Embedded image

Embedded image

Embedded image (Here, R8 and R9 are the same as those in formula (III). R10 and R11 are monovalent lower alkyl groups, and
c is an acetyl group. ) Silicone rubbers that undergo such condensation-type crosslinking include
Metal carboxylates of tin, zinc, lead, calcium, manganese, etc., such as dibutyltin laurate, tin (II) octate, naphthenates, etc., or catalysts such as chloroplatinic acid are added.

Further, the following expression (V
Examples of the silicone rubber layer crosslinked by the addition reaction of (II) and (VIII) include a polyvalent hydrogenorganopolysiloxane and two or more compounds represented by formula (VII) in one molecule.
I) A composition obtained by reaction with a polysiloxane having a bond, and preferably obtained by crosslinking and curing a composition comprising the following components. Such silicone rubber is a photodimerizable reactive group (for example, the one used in the above-mentioned photosensitive layer).
May be included.

[0061]

Embedded image -CH = CH- (VIII) (1) 100 parts by weight of organopolysiloxane having at least two alkenyl groups (preferably vinyl groups) directly bonded to silicon atoms in one molecule (2) at least one compound represented by the formula ( VII) Organohydrogenpolysiloxane having two groups 0.1 to 1000 parts by weight (3) Addition catalyst 0.00001 to 10 parts by weight The alkenyl group of the component (1) may be at the end of the molecular chain or in the middle. Also, as the organic group other than the alkenyl group,
It is a substituted or unsubstituted alkyl group or aryl group.
The component (1) may have a small amount of hydroxyl groups. Component (2) reacts with component (1) to form a silicone rubber layer,
It plays a role of imparting adhesiveness to the photosensitive layer. The hydrogen group of the component (2) may be at the terminal of the molecular chain or at the middle, and the organic group other than hydrogen is selected from those similar to the component (1). It is preferable that 60% or more of the organic groups of the component (1) and the component (2) are methyl groups as a whole in view of improvement of ink repellency. Component (1) and component (2)
The molecular structure of may be linear, cyclic or branched, and it is preferable that at least one of them has a molecular weight of more than 1000 from the viewpoint of rubber physical properties, and it is more preferable that the molecular weight of component (2) exceeds 1,000. . Examples of the component (1) include α, ω-divinylpolydimethylsiloxane and a (methylvinylsiloxane) (dimethylsiloxane) copolymer having methyl groups at both ends, and the component (2) has a hydrogen group at both ends. Polydimethylsiloxane, α, ω-
Examples thereof include dimethyl polymethyl hydrogen siloxane, (methyl hydrogen siloxane) (dimethyl siloxane) copolymer having methyl groups at both ends, and cyclic polymethyl hydrogen siloxane. The addition catalyst of the component (3) is arbitrarily selected from known ones, but a platinum-based compound is particularly preferable, and platinum simple substance, platinum chloride, chloroplatinic acid, olefin coordinated platinum and the like are exemplified. For the purpose of controlling the curing speed of these compositions, vinyl group-containing organopolysiloxanes such as tetracyclo (methylvinyl) siloxane, carbon-carbon triple bond-containing alcohols,
It is also possible to add a crosslinking inhibitor such as acetone, methyl ethyl ketone, methanol, ethanol and propylene glycol monomethyl ether. These compositions have the characteristic that, when the three components are mixed, an addition reaction occurs and curing starts, but the curing rate increases rapidly as the reaction temperature increases. Therefore, for the purpose of prolonging the pot life of the composition until it becomes rubber, and shortening the curing time on the photosensitive layer, the curing conditions of the composition are temperature conditions in which the characteristics of the substrate and the photosensitive layer do not change, Further, it is preferable to keep the temperature at a high temperature until it is completely cured, from the viewpoint of stability of the adhesive force with the photosensitive layer.

In addition to these compositions, a known adhesion-imparting agent such as alkenyltrialkoxysilane may be added, or a hydroxyl group-containing organopolysiloxane or a hydrolyzable functional group which is a composition of a condensation type silicone rubber layer. It is optional to add the silane (or siloxane) contained therein, and it is also optional to add a known filler such as silica for the purpose of improving the rubber strength.

The thickness of these silicone rubber layers is 0.5.
.About.50 g / m @ 2, more preferably 0.5.about.
It is 10 g / m @ 2.

In some cases, a fluororesin may be used as the ink repellent layer instead of the silicone rubber as shown above. Examples of such a fluororesin include, but are not limited to, the followings.

(1) Perfluoroalkyl methacrylate and an acrylic monomer having a hydroxy group, for example, 2-
Copolymer resin with hydroxyethyl methacrylate.

(2) A copolymer resin of perfluoroalkyl methacrylate and glycidyl methacrylate.

(3) Copolymer resin of perfluoroalkyl methacrylate and methacrylic acid.

(4) Copolymer resin of perfluoroalkyl methacrylate and maleic anhydride.

When such a fluororesin has both an active hydrogen functional group and a functional group capable of reacting with active hydrogen, or a fluororesin having an active hydrogen functional group and a fluorine having a functional group capable of reacting with active hydrogen. When the resin is mixed and used, a cross-linking agent may be used. Such a fluororesin may contain a photodimerizable reactive group (for example, the one used in the above-mentioned photosensitive layer).

The thickness of the fluororesin layer is about 0.5 to 100 g.
/ M @ 2, preferably about 0.5 to 10 g / m @ 2, when too thin, problems may occur in printing durability and ink repulsion, while when too thick, it is economically disadvantageous. Not only that, it becomes difficult to remove the fluororesin layer at the time of development, resulting in deterioration of image reproducibility.

The mixing ratio of each component in the fluororesin layer is not particularly limited, but the above-mentioned fluororesin may be used in a total amount of 6%.
The amount is preferably 0 to 100% by weight, more preferably 80 to 98% by weight based on the total weight.

The ink-repellent layer forming the surface of the waterless lithographic printing plate precursor thus constructed has ink-repellent properties, and the surface thereof has some tackiness and dust or the like adheres thereto. Cheap. For this reason, in the exposure step, problems such as difficulty in sufficiently adhering the positive film or the negative film are likely to occur. Therefore, it is important to attach a thin transparent protective film to the surface of the ink repellent layer.

Specific examples of such a protective film include polyethylene, polypropylene, polyvinyl chloride,
Examples thereof include polyvinylidene chloride, polyvinyl alcohol, polyethylene terephthalate and cellophane. Further, in order to improve the vacuum adhesion in the baking frame at the time of image exposure, it is also preferable that these protective films are matt-treated on the surface or a plastic layer containing silica particles or the like is applied and laminated on the surface of the protective film. Done.

Next, the method for producing the waterless planographic printing plate precursor according to the invention will be described. An ordinary coater such as a reverse roll coater, an air knife coater, and a Mayer bar coater, or a spin coater such as a whaler was used to apply a primer layer composition to the substrate as needed, followed by curing at 100 to 300 ° C. for several minutes. After that, the photosensitive layer composition coating liquid is applied, dried at a temperature of 50 to 150 ° C. for several minutes, and thermally cured if necessary, and the ink repellent composition is applied thereon, and the temperature of 50 to 150 ° C. for several minutes. It is formed by heat treatment and rubber curing. After that, a protective film is laminated if necessary.

Next, the exposure and development process of the waterless planographic printing plate precursor according to the invention will be described.

The waterless planographic printing plate referred to in the present invention is preferably used as a plate material for positive working.
The plate material is image-exposed with a usual exposure light source through a positive film which is vacuum-contacted. Examples of the light source used in the exposure step include a high-pressure mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, a fluorescent lamp, and the like. After such normal exposure, the plate surface is rubbed with a developing pad or brush containing a developer described below, the ink repellent layer in the unexposed area is removed to expose the photosensitive layer, and the ink receiving part ( The image area) is exposed and becomes a printing plate.

As the developing solution used in the present invention, a known developing solution can be used, and a developing solution capable of appropriately dissolving or swelling the photosensitive layer is preferable. Also, it is naturally preferable to swell the ink repellent layer. For example, aliphatic hydrocarbons (hexane, heptane, “isopar E, H, G” (ESSO
(Product name of isoparaffin hydrocarbons made from gasoline, gasoline, kerosene, etc.), aromatic hydrocarbons (toluene, xylene, etc.), halogenated hydrocarbons (tricrene, etc.), etc. The thing which added at least 1 sort (s) of a polar solvent is used preferably.

Alcohols (methanol, ethanol,
Propanol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol,
Tripropylene glycol, polypropylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, hexylene glycol, 2-ethyl-1,3
-Hexanediol, etc.) Ethers (ethylene glycol monoethyl ether,
Diethylene glycol, monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol mono-
2-ethylhexyl ether, triethylene glycol monoethyl ether, tetraethylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, dioxane,
Tetrahydrofuran, etc. Ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, etc.) Esters (ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, butyl lactate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, Diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether ateate, etc.) Carboxylic acid (2-ethylbutyric acid, caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, oleic acid,
(Lauric acid, etc.) In addition, water or a known surfactant may be freely added to the above organic solvent-based developer composition. In addition, an alkaline agent such as sodium carbonate,
Monoethanolamine, diethanolamine, triethanolamine, sodium silicate, potassium silicate, potassium hydroxide, sodium borate and the like can also be added.

Further, well-known basic dyes such as crystal violet, Victoria Pure Blue, and Astrazone Red, acid dyes, and oil-soluble dyes may be added to these developers to dye the image area at the same time as development. it can.

When developing the waterless planographic printing plate used in this study, an automatic developing machine commercially available from Toray Co., Ltd. is used, and the plate surface is pretreated with the above developing solution. After that, the plate surface is rubbed with a rotating brush while showering with tap water or the like, so that suitable development can be performed. Further, development can also be performed by spraying hot water or water vapor on the plate surface instead of the above-mentioned developer.

[0081]

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

Example 1 On a degreased aluminum plate having a thickness of 2.4 mm, a primer solution having the following composition was applied, dried at 230 ° C. for 1 minute, and dried to 3 g.
A primer layer of / m @ 2 was provided.

(1) Cancoat 90T-25-3094 (Kansai Paint Co., Ltd., epoxy phenol resin) 20 parts by weight (2) Dimethylformamide 80 parts by weight A photosensitive solution having the following composition is applied onto this primer layer. Then, it was dried at 100 ° C. for 1 minute to form a photosensitive layer having a thickness of 4 g / m 2.

(1) Esterification product of cinnamic acid and hydroxyethyl acrylate 20 parts by weight (2) Polyester polyol consisting of adipic acid and polyethylene glycol and polyurethane of isophorone diisocyanate 50 parts by weight (3) Tripropylene glycol diglycidyl ether 1 5 parts by weight of addition reaction product of mol and 2 mol of acrylic acid (4) N, N'-di- (2-hydroxy-3-methacryloyloxypropyl) -N'-di- (2-hydroxy-3-butoxy) Propyl) m-xylylenediamine 10 parts by weight (5) 4,4'-bis (diethylamino) benzophenone 5 parts by weight (6) N-methylacridone 9.7 parts by weight (7) Crystal violet 0.3 parts by weight (8) ) Ethyl cellosolve 400 parts by weight Then, on the photosensitive layer The silicone rubber solution having a formed coating, 120 ° C., and dried for 2 minutes, the thickness of 2g
A silicone rubber layer of / m @ 2 was provided.

(1) 100 parts by weight of silanol polydimethylsiloxane having both terminals (number average molecular weight of 100,000) (2) 12 parts by weight of ethyltriacetoxysilane (3) 0.1 parts by weight of dibutyltin diacetate (4) Isopar E 750 parts by weight On the surface of the silicone rubber layer obtained as described above,
A composite film "YM-70" (manufactured by Toray Industries, Inc.) having a thickness of 15 microns was laminated to obtain a waterless planographic printing plate precursor.

A gradation positive film having a halftone dot of 2% to 98% at 175 lines / inch was vacuum adhered to this lithographic printing plate precursor at a vacuum degree of 750 mmHg for 30 seconds,
It was exposed for 90 seconds from a distance of 1 m with a 3 Kw ultra-high pressure mercury lamp (Oak Seisakusho). The laminate film was removed from the exposure plate, and diethylene glycol mono-2-ethylhexyl ether / 1,3-butylene glycol = 70/3
Toray waterless planographic automatic developing machine (TWL-11
Pretreatment temperature 3 in a pretreatment tank of 60 (manufactured by Toray Industries, Inc.)
Development was carried out at 5 ° C. and a conveyance speed of 100 cm / min to obtain a waterless planographic printing plate. (Tap water was used as the developing solution.) The obtained printing plate was subjected to an offset printing machine (Komori Sprint 4
It was attached to a color machine and printed on coated paper using "Dryo Color" indigo ink manufactured by Dainippon Ink and Chemicals, Inc. When 150 lines / inch halftone dots of 2% to 98% were reproduced. A print with a good image was obtained.

On the other hand, a positive film having a pattern of 150 lines / inch was adhered to the lithographic printing plate precursor, exposed with a 3 Kw ultra-high pressure mercury lamp (Oak Seisakusho) from a distance of 1 m for 90 seconds, and developed by the above method. A waterless planographic printing plate was obtained.
The obtained printing plate is used for commercial off-wheel printing press (LITHOPI
A manufactured by Dainippon Ink and Chemicals Co., Ltd. using "Dry color" black ink, indigo, red, yellow ink, 800 r. p. As a result of printing durability test after printing on high-quality paper at a speed of m, a good printed material was obtained even after printing 200,000 copies, and the printing plate after the printing was inspected, but the printing plate was found to be slightly damaged. It was

Example 2 Printing was carried out in the same manner as in Example 1 except that the esterified product of cinnamic acid and hydroxyethyl acrylate in the photosensitive layer was changed to the reaction product of cinnamic acid and glycidyl methacrylate. A plate precursor was prepared, and exposure, development, image evaluation and printing durability test were conducted in the same manner as in Example 1. In the image evaluation, a printed matter having a very good image in which 2% to 98% of dots at 150 lines / inch was reproduced was obtained.
In the printing durability test, good printed matter was obtained even after printing 200,000 copies, and the printing plate after the printing was inspected, but the printing plate was found to be slightly damaged.

Example 3 In Example 1, the esterified product of cinnamic acid and hydroxyethyl acrylate in the photosensitive layer was changed to a reaction product of cinnamic acid and epichlorohydrin, and N-methylacridone was replaced with benzointosine. Example 1 except that the rate is changed
A printing plate precursor was prepared in the same manner as in, and exposure, development, image evaluation, and printing durability test were performed in the same manner as in Example 1. In the image evaluation, a printed matter having a very good image in which 2% to 98% of dots at 150 lines / inch was reproduced was obtained. In the printing durability test, good printed matter was obtained even after printing 200,000 copies, and the printing plate after the printing was inspected, but the printing plate was found to be slightly damaged.

Example 4 Except that in Example 1, the esterified product of cinnamic acid and hydroxyethyl acrylate in the photosensitive layer was changed to a compound obtained by reacting 1 mol of glycerin with 1 mol of cinnamic acid and 2 mols of acrylic acid. A printing plate precursor was prepared in the same manner as in Example 1, and exposure, development, image evaluation and printing durability test were performed in the same manner as in Example 1. In the image evaluation, a printed matter having a very good image in which 2% to 98% of dots at 150 lines / inch was reproduced was obtained. In the printing durability test, 20
A good printed matter was obtained even after printing of 10,000 copies, and the printing plate after the printing was inspected, but the printing plate was found to be slightly damaged.

Comparative Example 1 In Example 1, N, N′-di- (2-hydroxy-3-methacryloyloxypropyl) -N ′ was removed except for the esterification product of cinnamic acid and hydroxyethyl acrylate in the photosensitive layer. 10 parts by weight of di- (2-hydroxy-3-butoxypropyl) m-xylylenediamine
A printing plate precursor was prepared in the same manner as in Example 1 except that the amount was changed to parts by weight, and exposure, development, image evaluation, and printing durability test were performed in the same manner as in Example 1. In the image evaluation, 150
Lines / inch halftone dots yielded only prints with 5% to 95% reproduction. In the printing durability test, 10
The printing plate was severely damaged at the printing stage of 10,000 copies.

Example 5 A degreased aluminum plate having a thickness of 2.4 mm was coated with a primer solution having the following composition, dried at 220 ° C. for 2 minutes, and then dried.
A primer layer of g / m @ 2 was provided.

(1) Polyurethane resin (Sampren LQ-SZ18, manufactured by Sanyo Chemical Co., Ltd.) 100 parts by weight (2) Blocked isocyanate (Taketate B830, manufactured by Takeda Pharmaceutical Co., Ltd.) 30 parts by weight (3) Epoxy / phenol / urea Resin (SJ9372, manufactured by Kansai Paint Co., Ltd.) 10 parts by weight (4) Dimethylformamide 700 parts by weight A photosensitive solution having the following composition is applied on this primer layer, dried at 120 ° C. for 1 minute, and a thickness of 3 g. A photosensitive layer of / m @ 2 was provided.

(1) Esterification product of cinnamic acid and hydroxyethyl acrylate / glycidyl acrylate = 50/50 copolymer (number average molecular weight 9000) 30 parts by weight (2) adipic acid and hexane-1,6-diol Polyurethane obtained by reacting polyester polyol with 2,2-dimethylpropane-1,3-diol and isophorone diisocyanate 10 parts by weight (3) m-xylylenediamine / glycidyl methacrylate / methylglycidyl ether = 1/2 / 2 addition reaction product 20 parts by weight (4) Michler's ketone 3 parts by weight (5) Benzoin tosylate 5 parts by weight (6) Victoria Pure Blue BOH naphthalene sulfonic acid 0.7 parts by weight (7) Phthalic acid 1.3 parts by weight Parts (8) Tetrahydrofuran 530 parts by weight Subsequently, The photosensitive layer silicone rubber solution having the following composition was coated on the, 110 ° C., and dried for 2 minutes, a thickness of 1.
A 5 g / m @ 2 silicone rubber layer was provided.

(1) Polydimethylsiloxane with vinyl groups on both ends (number average molecular weight 100,000) 100 parts by weight (2) 1,1,2-trimethyldisilane 19.5 parts by weight (3) Platinum chloroplatinate / methyl vinyl chloride Click complex 0.5 parts by weight (4) Toluene 780 parts by weight On the surface of the silicone rubber layer obtained as described above,
A composite film "YM-70" (manufactured by Toray Industries, Inc.) having a thickness of 15 microns was laminated to obtain a waterless planographic printing plate precursor.

A gradation positive film having a halftone dot of 2% to 98% at 175 lines / inch was vacuum adhered to this lithographic printing plate precursor at a vacuum degree of 750 mmHg for 30 seconds,
It was exposed for 90 seconds from a distance of 1 m with a 3 Kw ultra-high pressure mercury lamp (Oak Seisakusho). The laminate film was removed from the exposure plate, and diethylene glycol mono-2-ethylhexyl ether / 1,3-butylene glycol = 70/3
Toray waterless planographic automatic developing machine (TWL-11
60, pretreatment temperature 3 in a pretreatment tank manufactured by Toray Industries, Inc.
Development was carried out at 5 ° C. and a conveyance speed of 100 cm / min to obtain a waterless planographic printing plate. (Tap water was used as the developing solution.) The obtained printing plate was attached to an offset printing machine (Komori Sprint 4-color machine), and "Dry color" indigo ink manufactured by Dainippon Ink and Chemicals, Inc. was used. When printing was performed on the coated paper, a printed matter having an extremely good image in which 2% to 98% of halftone dots of 150 lines / inch was reproduced was obtained.

On the other hand, a positive film with a pattern of 150 lines / inch was adhered to the lithographic printing plate precursor, exposed with a 3 Kw ultra-high pressure mercury lamp (Oak Seisakusho) from a distance of 1 m for 90 seconds, and developed by the above method. Then, a waterless planographic printing plate was obtained.
The obtained printing plate is used for commercial off-wheel printing press (LITHOPI
A manufactured by Dainippon Ink and Chemicals Co., Ltd. using "Dry color" black ink, indigo, red, yellow ink, 800 r. p. As a result of printing on a high-quality paper at a speed of m and performing a printing durability test, good printed matter was obtained even after printing 190,000 copies, and the damage to the printing plate after printing was slight.

Example 6 In Example 5, a copolymer of cinnamic acid and hydroxyethyl acrylate ester / glycidyl acrylate = 50/50 in the photosensitive layer (number average molecular weight 9000)
Was changed to a copolymer of cinnamic acid and hydroxyethyl acrylate / glycidyl methacrylate = 50/50 copolymer (number average molecular weight 8000) to prepare a printing plate precursor in the same manner as in Example 5, and In the same manner as in No. 5, exposure, development, image evaluation and printing durability test were performed. In the image evaluation, a printed matter having a very good image in which 2% to 98% of dots at 150 lines / inch was reproduced was obtained.
In the printing durability test, good printed matter was obtained even after printing 190,000 copies, and the printing plate after completion of printing was inspected, but the printing plate was found to be slightly damaged.

Example 7 In Example 5, a copolymer of cinnamic acid and hydroxyethyl acrylate ester / glycidyl acrylate = 50/50 in the photosensitive layer (number average molecular weight 9000)
55% acrylic group on the glycidyl group of this polymer
A printing plate precursor was prepared in the same manner as in Example 5 except that the introduced compound was changed and benzoin tosylate was changed to thioxanthone, and exposure, development, image evaluation, and printing durability test were performed in the same manner as in Example 5. went. Image evaluation is 1
Prints were obtained with very good images with 50% line / inch dots reproduced from 2% to 98%. In the printing durability test, good printed matter was obtained even after printing 190,000 copies, and the printing plate after completion of printing was inspected, but the printing plate was found to be slightly damaged.

Comparative Example 2 In Example 5, except for the cinnamic acid / hydroxyethyl acrylate ester / glycidyl acrylate = 50/50 copolymer (number average molecular weight 9000) in the photosensitive layer in the photosensitive layer To N, N'-di- (2-hydroxy-3-methacryloyloxypropyl) -N '
-Di- (2-hydroxy-3-butoxypropyl) m-
A printing plate precursor was prepared in the same manner as in Example 5 except that 30 parts by weight of xylylenediamine was added, and exposure, development, image evaluation and printing durability test were performed in the same manner as in Example 5. In the image evaluation, 150 lines / inch halftone dots are 5% to 95%.
Only the printed matter that was reproduced was obtained. In the printing durability test, the printing plate was severely damaged at the printing stage of 80,000 copies.

Example 8 In Example 5, instead of polydimethylsiloxane having vinyl groups at both ends (number average molecular weight 100,000), a polydimethylsiloxane having vinyl groups at both ends-methylcinamoylsiloxane copolymer (number average molecular weight 40) was used. , 000, cinnamoyl group is about 5% of the total substituents), a printing plate precursor was prepared in the same manner as in Example 5, and the exposure, development, image evaluation and printing durability test were conducted in the same manner as in Example 5. I went. In the image evaluation, the dot density of 150 lines / inch is 2% to 9%.
Prints with very good images with 8% reproduction were obtained. In the printing durability test, good printed matter was obtained even after printing 210,000 copies, and the printing plate after completion of printing was inspected, but the printing plate was found to be slightly damaged.

Example 9 A printing plate precursor was prepared in the same manner as in Example 5 except that the photosensitive layer was changed as follows. Exposure, development and image evaluation were carried out in the same manner as in Example 5. A printing durability test was conducted. In the image evaluation, a printed matter having a very good image in which 2% to 98% of dots at 150 lines / inch was reproduced was obtained. In the printing durability test, good printed matter was obtained even after printing 210,000 copies, and the printing plate after completion of printing was inspected, but the printing plate was found to be slightly damaged.

(1) Polymer of esterified product of cinnamic acid and hydroxyethyl acrylate (number average molecular weight: 8000) 25 parts by weight (2) adipic acid and hexane-1,6-diol, 2,2-dimethylpropane- Polyurethane obtained by reacting polyester polyol with 1,3-diol and isophorone diisocyanate 10 parts by weight (3) m-xylylenediamine / glycidyl methacrylate / methyl glycidyl ether = 1/2/2 addition reaction product 25 parts by weight (4) Michler's Ketone 3 parts by weight (5) Benzointosylate 5 parts by weight (6) Victoria Pure Blue BOH Naphthalene Sulfonic Acid 0.7 parts by weight (7) Phthalic Acid 1.3 parts by weight (8) Tetrahydrofuran 530 parts by weight Example 10 In Example 9, the photosensitive layer was prepared as follows. A printing plate precursor was prepared in the same manner as in Example 9 except for changes, and exposure, development, image evaluation, and printing durability test were performed in the same manner as in Example 9. In the image evaluation, a printed matter having a very good image in which 2% to 98% of dots at 150 lines / inch was reproduced was obtained. In the printing durability test, good printed matter was obtained even after printing 220,000 copies, and the printing plate after the printing was inspected, but the printing plate was found to be slightly damaged.

(1) Polymer of esterified product of cinnamic acid and hydroxyethyl methacrylate (number average molecular weight 8200) 25 parts by weight (2) 1 mol of 1,6-hexanediamine and 2 mol of glycidyl methacrylate and 2 mol of methylglycidyl ether 25 parts by weight of a compound obtained by reacting moles (3) Polyurethane obtained by reacting a polyester polyol of adipic acid with hexane-1,6-diol or 2,2-dimethylpropane-1,3-diol and isophorone diisocyanate 10 parts by weight (4) Michler's ketone 3 parts by weight (5) Benzoin tosylate 5 parts by weight (6) Victoria Pure Blue BOH naphthalene sulfonic acid 0.7 parts by weight (7) Phthalic acid 1.3 parts by weight (8) Tetrahydrofuran 530 parts by weight Example 11 In Example 9 A printing plate precursor was prepared in the same manner as in Example 9 except that the photosensitive layer was changed as follows, and exposure, development, image evaluation, and printing durability test were performed in the same manner as in Example 9. In the image evaluation, a printed matter having a very good image in which 2% to 98% of dots at 150 lines / inch was reproduced was obtained. In the printing durability test, good printed matter was obtained even after printing 230,000 copies, and the printing plate after completion of printing was inspected, but the printing plate was found to be slightly damaged.

(1) Polymer of esterified product of cinnamic acid and hydroxyethyl acrylate (number average molecular weight of 8000) 20 parts by weight (2) 1 mol of glycerin was reacted with 3 mol of epichlorohydrin to obtain a compound. 30 parts by weight of a compound obtained by reacting 1 mol of a product with 3 mol of acrylic acid (3) Polyester polyol of adipic acid and hexane-1,6-diol, 2,2-dimethylpropane-1,3-diol, and isophorone diisocyanate Polyurethane obtained by the reaction of 10 parts by weight (4) Michler's ketone 3 parts by weight (5) Benzoin tosylate 5 parts by weight (6) Victoria Pure Blue BOH naphthalene sulfonic acid 0.7 parts by weight (7) Phthalic acid 1. 3 parts by weight (8) Tetrahydrofuran 530 parts by weight Comparative Example 3 Compound 1 obtained by reacting 1 mol of glycerin with 3 mol of epichlorohydrin in the layer
Except for the compound obtained by reacting 3 moles of acrylic acid with moles, the polymer of the esterified product of cinnamic acid and hydroxyethyl acrylate (number average molecular weight 8000) was changed from 20 parts by weight to 50 parts by weight to enable photodimerization. A printing plate precursor was prepared in the same manner as in Example 11 except that a photosensitive layer containing only a compound was prepared, and exposure, development, and
Image evaluation and printing durability test were performed. In image evaluation, 150
Lines / inch halftone dots yielded only prints with 5% to 95% reproduction. In the printing durability test, 7
The printing plate was severely damaged at the printing stage of 10,000 copies.

[0106]

According to the present invention, the photosensitive layer contains a compound having at least one photodimerizable reactive group and at least one photopolymerizable reactive group, or at least one photodimerizable reactive group. Since it has at least one compound having one and at least one compound having at least one photopolymerizable reactive group, it compensates for the low polymerization efficiency at low temperature which is a drawback of the photopolymerizable photosensitive layer. The weak adhesiveness between the photosensitive layer and the ink-repellent layer, which is a defect of the photodimerization type photosensitive layer, can be compensated, and the entire photosensitive layer after exposure is not as hard and brittle as the photopolymerizable type photosensitive layer, resulting in image reproducibility. It is possible to provide a waterless lithographic printing plate precursor having excellent printing durability and excellent solvent resistance.

Claims (11)

[Claims] 1. A waterless lithographic printing plate precursor in which a photosensitive layer and an ink repellent layer are sequentially laminated on a support, wherein the photosensitive layer has at least one photodimerizable reactive group and at least one photopolymerizable reactive group. A waterless lithographic printing plate precursor comprising a compound having each of 2. A waterless lithographic printing plate precursor in which a photosensitive layer and an ink repellent layer are sequentially laminated on a support, and the photosensitive layer is a photopolymerizable reactive group with a compound having at least one photodimerizable reactive group. A waterless lithographic printing plate precursor comprising at least one compound having at least one of 3. The waterless lithographic printing plate precursor according to claim 1 or 2, wherein the photodimerizable reactive group is a photodimerizable unsaturated double bond. 4. The waterless planographic printing plate precursor according to claim 1, wherein the photopolymerizable reactive group is a photopolymerizable unsaturated double bond. 5. The waterless lithographic printing plate precursor as claimed in claim 1, wherein the photodimerizable reactive group is represented by the following general formula (I). Embedded image (In the formula, R1 to R4 are each independently a hydrogen atom, an amino group, a nitro group, a hydroxyl group, a mercapto group, a halogen atom,
A substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, an alkoxy group, a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms, an alkenyloxy group, a substituted or unsubstituted aryl group having 4 to 50 carbon atoms, aryl At least one selected from the group of oxy groups, an ether bond, an ester bond, a carbonate bond, a urethane bond, in the chain,
It may contain at least one selected from the group consisting of a urea bond, an amide bond, a thioether bond, an amino bond and a carbonyl bond. R5 and R6 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, an alkoxy group, a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms, an alkenyloxy group, or 4 to 4 carbon atoms.
It is at least one selected from the group of 50 substituted or unsubstituted aryl groups and aryloxy groups, and has an ether bond, an ester bond, a carbonate bond, a urethane bond, a urea bond, an amide bond, a thioether bond, an amino bond, in the chain. It may contain at least one selected from the group of carbonyl bonds. ) 6. A compound having a photodimerizable reactive group,
Waterless lithographic printing according to any one of claims 1 to 5, which is a polymer compound having a structure represented by the general formula (I) in a main chain or a side chain and having a molecular weight of 500 to 5,000,000. Original edition. 7. The waterless lithographic printing plate precursor as claimed in claim 1, wherein the ink repellent layer has a photodimerizable reactive group. 8. The waterless lithographic printing plate precursor according to claim 7, wherein the photodimerizable reactive group of the ink repellent layer is represented by the following general formula (II). Embedded image (In the formula, R1 to R6 are independently the same as in the general formula (I).) 9. The waterless planographic printing plate according to claim 1, wherein the ink repellent layer is a silicone rubber layer crosslinked by a condensation reaction between a SiOH group and a hydrolyzable crosslinking agent. Original version. 10. The ink repellent layer comprises SiH groups and --CH═CH.
A waterless lithographic printing plate precursor according to any one of claims 1 to 8, which is a silicone rubber layer crosslinked by an addition reaction with a group. 11. A waterless planographic printing plate obtained by selectively exposing and developing the waterless planographic printing plate precursor according to any one of claims 1 to 10.