JPH08220739A - Waterless planographic printing master plate - Google Patents

Abstract

PURPOSE: To obtain a waterless planographic printing plate excellent in resistance to plate wear which is suitable for commercial web-fed offset press. CONSTITUTION: This waterless planographic printing plate consists of a photosensitive layer and ink-repelling layer deposited in this order on a support. The photosensitive layer contains at least the following components. (1) Amine polybutadiene having polymerizable ethylenic unsatd. groups, (2) polymer compd. having film-forming property except for the compd. (1), and (3) photopolymn. initiator.

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 precursor excellent in printing durability and image reproducibility. It is about.

[0002]

2. Description of the Related Art Various waterless lithographic printing plates having a silicone rubber layer as an ink repellent layer have already been proposed. Among them, a waterless planographic printing plate in which a photopolymerizable adhesive layer and a silicone rubber layer are laminated on a substrate proposed in Japanese Patent Publication No. 54-26923 or Japanese Patent Publication No. 56-23150, and Japanese Patent Publication No. 3-56622. JP-A No. 61-54218, and a waterless planographic printing plate in which a photodimerization type photosensitive layer and a silicone rubber layer are laminated on a substrate proposed in JP-A No. 61-153655 and JP-A No. 61-54218.
Proposed in Japanese Patent Publication No. 61-54222, or a waterless lithographic printing plate in which a silicone rubber layer is provided via an adhesive layer on a photosensitive layer containing an orthoquinonediazide compound backed by a support. A waterless planographic printing plate having a silicone rubber layer on the light-peelable photosensitive layer enables practical printing without using dampening water.

However, when the waterless planographic printing plates described in the above publications were subjected to offset printing, the publications of JP-B-54-26923 and JP-B-56-
In the waterless lithographic printing plate described in Japanese Patent No. 23150, it was found that high printing durability cannot be obtained due to destruction at the adhesive interface between the photosensitive layer and the silicone rubber layer.

Further, in the waterless lithographic printing plate using the photodimerization type photosensitive layer described in JP-A-3-56622 and JP-A-61-153655, the adhesive force between the photosensitive layer and the silicone rubber layer. It was found that the high printing durability could not be obtained because the silicone rubber layer fell off due to the small size.

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 silicone rubber layer is formed. It has been found that there is a problem that cracks occur 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-6-67411, a diamine compound at both terminals is reacted with glycidyl methacrylate to improve the sensitivity of the printing plate. But,
Although this method surely increases the sensitivity, it was found from the above-mentioned printing durability test results that high printing durability cannot be obtained due to breakage at the adhesive interface between the photosensitive layer and the silicone rubber layer.

[0007]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to incorporate a photosensitive compound having a specific structure into a photosensitive layer, and further to make the photosensitive layer elastic modulus, elongation at break, 50%.
By defining by the stress, the problems of the prior art as described above are solved, and even when it is used in the field of commercial off-wheel printing, it has excellent printing durability and excellent image reproducibility. It is to provide the original planographic printing plate.

[0008]

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

(1) A waterless planographic printing plate precursor in which a photosensitive layer and an ink repellent layer are sequentially laminated on a support, wherein the photosensitive layer contains at least the following components.

Polymerized compound having an aminated butadiene film-forming ability other than a photopolymerization initiator (2) The polymerizable group is an ethylenically unsaturated group, described in (2). Waterless planographic printing plate original.

(3) The waterless lithographic printing plate precursor as described in (1), wherein the aminated polybutadiene having a polymerizable group is an intramolecular aminated polybutadiene.

(4) The waterless planographic printing plate precursor as described in (1), wherein the aminated polybutadiene having a polymerizable group has a number average molecular weight of 500 to 8000.

(5) The waterless planographic printing plate precursor as described in any of (1) to (4), wherein the photosensitive layer is a photopolymerizable photosensitive layer.

(6) The photosensitive layer contains a compound having at least one amino group structure and at least one ethylenically unsaturated bond, respectively. (1) to (5) Waterless planographic printing plate original.

(7) The photosensitive layer has at least one amino group structure and at least one ethylenically unsaturated bond,
The waterless planographic printing plate precursor as described in any one of (1) to (6), which further comprises a compound having at least one hydroxyl group.

(8) The photosensitive layer contains a compound not having an amino group structure and having at least one ethylenically unsaturated bond (1) to (1)
The waterless planographic printing plate precursor as described in any of (7).

(9) The photosensitive layer contains a compound having no amino group structure, at least one ethylenically unsaturated bond, and at least one hydroxyl group. A waterless planographic printing plate precursor as described in any one of (1) to (8), which is characterized.

(10) The initial elastic modulus of the photosensitive layer after exposure is 5
~ 75 kgf / mm2 (1) ~
The waterless planographic printing plate precursor as described in any of (9).

(11) The elongation at break of the photosensitive layer after exposure is 10
The waterless planographic printing plate precursor as described in any one of (1) to (10), which is 0% or more.

(12) The waterless planographic printing plate precursor as described in any one of (1) to (11), wherein the 50% stress after exposure of the photosensitive layer is 0.5 to 3.8 kgf / mm 2. .

(13) The waterless layer according to any one of (1) to (12), 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 planographic printing plate.

(14) The ink repellent layer contains SiH groups and --CH.
A waterless lithographic printing plate precursor as described in any of (1) to (12), which is a silicone rubber layer crosslinked by an addition reaction with a = CH- group.

(15) A waterless planographic printing plate obtained by selectively exposing and developing the waterless planographic printing plate precursor described in any one of (1) to (14).

[0024]

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. Of these supports, the aluminum plate is particularly preferable because it is remarkably dimensionally stable 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 photocurable 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 as a coating layer is 0.5 to
50 g / m @ 2 is preferred, more preferably 1-10 g / m @ 2
m2.

The photosensitive layer used in the present invention is generally any as long as it causes a difference in solubility in a developing solution upon exposure or causes a change in adhesiveness at the interface with the upper ink repellent layer. Even if it is one, it can be used, but it contains at least the following components.

(1) Aminated butadiene having a polymerizable group (2) Polymer compound other than (1) having film forming ability (3) Photopolymerization initiator Hereinafter, these three components will be described in order. .

Component (1): Aminated polybutadiene having a polymerizable group By containing the aminated polybutadiene having a polymerizable group, the polymer itself has a photoreactive group so that photocrosslinking can be efficiently performed. proceed. Further, since it has an amino group, the sensitivity is also increased. Further, since the photosensitive layer is softened, stress concentration on the plate surface is relieved, and printing durability is improved.

Here, examples of the aminated polybutadiene having a polymerizable group include those in which a polymerizable ethylenically unsaturated group is introduced into intramolecular aminated polybutadiene. Examples of the method of introducing the polymerizable ethylenically unsaturated group include a method of reacting glycidyl methacrylate or methacrylic acid chloride.

As the intramolecular aminated polybutadiene,
Intramolecular aminated polybutadiene having no amino groups at both ends and having a glass transition temperature of room temperature or lower is preferably used, but liquid aminated polybutadiene which is liquid at room temperature is preferably used.

The number average molecular weight of this liquid aminated polybutadiene is preferably 500 to 8,000, more preferably 700 to 6000. When the molecular weight is less than 500, the image reproducibility tends to decrease, and when it is more than 8000, the developability tends to decrease.

Such liquid aminated polybutadiene can be obtained by reacting liquid epoxidized polybutadiene with a primary or secondary diamine.

The liquid epoxidized polybutadiene preferably has a number average molecular weight of 500 to 5,000, more preferably 70.
It is 0 to 3500. If it is less than 500, the shape retention of the raw plate tends to deteriorate, and if it exceeds 5000, the handleability tends to deteriorate.

The epoxy equivalent of the liquid epoxidized polybutadiene is preferably 4000 or less.

Examples of such liquid epoxidized polybutadiene include epoxy compounds represented by the following general formula (I) or general formula (II).

[0041]

Embedded image (In the formula, each unit of a + b ≧ 1, a, b, c, d, and e represents a random or block-bonded unit. R1 and R
2 is an organic group having a functional group selected from a hydroxyl group, a carboxyl group, a phenol group, an acryloyl group, a methacryloyl group, an allyl group, a mercapto group, a dialkoxysilyl group, a silanol group, an epoxy group, an isocyanate group and a halogen group at the end. And R1 and R2 may be the same or different. X represents a polymerizable divalent linking group. )

Embedded image (In the formula, each unit of c, d, and e represents a random or block-bonded unit, and X represents a polymerizable divalent linking group.) In the general formula (I), a + b ≧ 1, a , B, c, d, and e represent random or block-bonded units.
a + b + c + d + e is preferably 1 to 40, the number average molecular weight is preferably 50 to 10,000, and more preferably 50.
It is 0 to 5000. Although the mol% of each unit a, b, c, d is arbitrary, in order to effectively express the effect of the present invention, the mol% of a + b is 1 to 80 mol%, more preferably 1 to 50 mol%. Is. R1 and R2 each have a functional group selected from a hydroxyl group, a carboxyl group, a phenol group, an acryloyl group, a methacryloyl group, an allyl group, a mercapto group, a dialkoxysilyl group, a silanol group, an epoxy group, an isocyanate group and a halogen group at the end. R is an organic group
1 and R2 may be the same or different. Preferably a hydroxyl group, a carboxyl group, a phenol group, an acryloyl group,
A methacryloyl group, an allyl group, and an epoxy group. X
Represents a polymerizable divalent linking group. The polymerizable divalent linking group represented by X preferably includes at least one monomer copolymerizable with butadiene such as styrene, (meth) acrylic acid, and acrylonitrile. The invention is not limited to these, and any polymerizable divalent linking group is used.

In the general formula (II), c + d + e is 1
The number average molecular weight is preferably from 50 to 10,000, more preferably from 500 to 5,000. Although the mol% of each unit c, d, and e is arbitrary, the mol% of c is 1 to 99 mol%, and more preferably 5 to 95 mol% in order to effectively exhibit the effects of the present invention. . X represents a polymerizable divalent linking group. The polymerizable divalent linking group represented by X preferably includes at least one monomer copolymerizable with butadiene such as styrene, (meth) acrylic acid, and acrylonitrile. The invention is not limited to these, and any polymerizable divalent linking group is used.

Specific product groups of the above general formula (I) include Denarex "R-15EPI" and "R-45EP".
I "(manufactured by Idemitsu Petrochemical Co., Ltd.)," E-1000-3.
5 "," E-1000-6.5 "," E-1000- "
8.0 "," E-1500-8.0 "," E-1800 "
-6.5 "(manufactured by Nippon Petrochemical Co., Ltd.)," BF-100 "
0 ”,“ BF-2000 ”,“ BF-3000 ”(manufactured by Nippon Soda Co., Ltd.) and the like, but the present invention is not limited to these examples.

Specific product groups of the above general formula (II) include, for example, "R-15EPT" and "R-45EP".
T "(manufactured by Idemitsu Petrochemical Co., Ltd.) and the like, but the present invention is not limited to these examples.

As the primary or secondary diamine, all commercially available primary or secondary diamines can be used, but dimethylaminopropylamine,
Diethylaminopropylamine, dibutylaminopropylamine, 3- (dibutylamino) propylamine,
4,4'-diaminodicyclohexylmethane, 3,3 '
-Dimethyl-4,4'-diaminodicyclohexylmethane, ethylenediamine, N, N-diethylethylenediamine, 1,2-propanediamine, pentamethylenediamine, stearylpropylenediamine, polyoxyethylenediamine, polyoxypropylenediamine and the like are preferable.

These primary or secondary diamines are
It is preferable to react 1 mol or more with respect to 1 mol of epoxidized polybutadiene. When the amount is less than 1 mol, the image reproducibility of the printing plate is deteriorated.

The amount of the aminated polybutadiene having a polymerizable group used is preferably 1 to 80% by weight, more preferably 5 to 60% by weight, based on the total photosensitive layer composition. When the amount used is less than 1% by weight, printing durability tends to decrease, and when it is more than 80% by weight, developability tends to decrease.

Component (2): polymer compound having film-forming ability As such polymer compound having film-forming ability, methacrylic acid copolymer, acrylic acid copolymer, crotonic acid copolymer, maleic acid Copolymer, partially esterified maleic acid copolymer, acidic cellulose derivative, polyvinylpyrrolidone, polyethylene oxide, alcohol-soluble nylon, polyester, unsaturated polyester, polyurethane, polystyrene, epoxy resin, phenoxy resin, polyvinyl butyral, polyvinyl formal,
Examples thereof include polyvinyl chloride, polyvinyl alcohol, partially acetalized polyvinyl alcohol, water-soluble nylon, water-soluble urethane resin, gelatin, water-soluble cellulose derivative and the like.

These polymer compounds capable of forming a film can be used alone or in combination of two or more. The amount of the polymer compound having a film-forming ability to be used is preferably 10 to 80% by weight, more preferably 30 to 70% by weight, based on the entire 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 80% by weight, the developability tends to be lowered.

Component (3): Photopolymerization Initiator As such a photopolymerization initiator, US Pat.
Vicinal polyketaldonyl compounds disclosed in US Patent No. 660, US Pat. Nos. 2,367,661 and 23.
67670, α-carbonyl compounds, US Pat. No. 2,488,828, acyloin ethers, US Pat. No. 2,722,512, and α-positions substituted with hydrocarbons. Aromatic acyloin compounds, polynuclear quinone compounds disclosed in U.S. Pat. No. 2,951,758, triaryl imidazole dimer / p-aminophenyl ketone combinations disclosed in U.S. Pat. No. 3,549,367, U.S. Pat. Benzothiazole compounds disclosed in US Pat. No. 3,870,524, US Pat. No. 423.
Benzothiazole compounds / trihalomethyl-s-triazine compounds disclosed in 9850 and acridine and phenazine compounds disclosed in U.S. Pat. No. 3,751,259, U.S. Pat. No. 42129.
Oxadiazole compounds disclosed in Japanese Patent No. 70, U.S. Pat. No. 3,954,475, JP-A-53-133
No. 428, U.S. Pat. No. 4,189,323, JP-A-60-
No. 105667, JP-A-63-153542, and trihalomethyl-s-triazine compounds having a chromophore group, JP-A-59-197401 and JP-A-60-76503. The benzophenone group-containing belloxy ester compound may be mentioned. 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 components, it is possible to add other polymerizable ethylenically unsaturated monomer or oligomer for the purpose of controlling image reproducibility. Examples of such polymerizable ethylenically unsaturated monomers include known amine-based monomers and non-amine-based monomers. Above all,
From the viewpoint of adhesion to the ink repellent layer of the upper layer, an amine-based monomer containing a hydroxyl group or a non-amine-based monomer is preferable, but not limited thereto.

Specific examples of the amine-based monomer 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-mentioned amine-based monomer, and any compound having at least one amino group structure and at least one ethylenically unsaturated bond may be used.

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
708, Japanese Patent Publication No. 48183/64183, Japanese Patent Publication No. 49-4
Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates obtained by reacting an epoxy resin with (meth) acrylic acid, which are described in JP-A No. 3191 and JP-B No. 52-3-490, can be mentioned. These are compounds having no amino group structure and having at least one ethylenically unsaturated bond, and some compounds further have at least one hydroxyl group.

The amount of the polymerizable ethylenically unsaturated monomer or oligomer used is 10 to 80 relative to the total composition of the photosensitive layer.
% By weight is preferred, more preferably 20-60% by weight
Is. When the amount used is less than 10% by weight, the image reproducibility of the plate decreases, and when it is more than 80% by weight, the storage stability of the plate decreases.

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 adhesiveness with the primer layer. Examples of such a diazo resin include those described in U.S. Pat. No. 3,867,147 and U.S. Pat. No. 2,632,703, and are particularly represented by a condensate of an aromatic diazonium salt and an active carbonyl-containing compound (formaldehyde, for example). Diazo resins are useful.
Preferred diazo resins include, for example, hexafluorophosphate, tetrafluoroborate, and phosphate of a condensate of p-diazodiphenylamine and formaldehyde or acetaldehyde. Also, US Pat.
No. 09, sulfonates of condensates of p-diazodiphenylamine and formaldehyde (eg p-toluenesulfonate, dodecylbenzenesulfonate, 2-methoxy-4-hydroxy-5-benzoylbenzenesulfone). Acid salts, etc.), phosphinates, organic carboxylates and the like are also preferable. The preferred amount of the diazo resin added is 0.1 to 5% by weight based on the total photosensitive layer composition.

Furthermore, 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 or a leuco dye as a printout agent 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 added is usually 10% by weight or less based on the total composition of the photosensitive layer.

In some cases, in order to enhance the adhesion to the ink repellent layer, silica powder or hydrophobic silica powder whose surface is treated with a (meth) acryloyl group- or allyl group-containing silane coupling agent is used for all photosensitive layers. 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 / mm @ 2, more preferably 10 to 50 kgf /
It is important that it is mm2. If the initial elastic modulus after exposure is less than 5 kgf / mm @ 2, the photosensitive layer becomes brittle and 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 ink repellent layer and the photosensitive layer. The resulting solution is filtered to separate the unwanted ink repellent layer in the soluble solvent. Further, the solution is concentrated under reduced pressure to a solid content of 30% 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.
A test piece was prepared from a 0 μm thick sheet with a No. 4 dumbbell, and exposed for 10 minutes with a UV meter (Oak Seisakusho Light Measure Type UV365) at 12 mW / cm 2 using a 3 kW ultra-high pressure mercury lamp (Oak Seisakusho). Then, using Tensilon RTM-100 (manufactured by Orientec Co., Ltd.), at a tensile speed of 20 cm / min, JIS
Initial elastic modulus, elongation at break, and 50% stress value are measured according to K6301.

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 from the viewpoint 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.

[0066]

Embedded image (In the formula, n is an integer of 2 or more. R5 and R6 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, R
5, 60% or more of R6 is preferably a methyl group.
Further, it has at least one hydroxyl group in the molecular chain in the form of a chain end or a side chain. ) In the case of the silicone rubber layer applied to the printing plate of the present invention, the silicone rubber (R
TV, LTV type silicone rubber) is used. As such a silicone rubber, R of an organopolysiloxane chain is used.
Although those in which a part of R6 and R6 are replaced by hydrogen atoms can also be used, they are usually crosslinked by condensation of terminal groups represented by the following formulas (IV), (V) and (VI). In some cases, an excess amount of the cross-linking agent may be present.

[0067]

[Chemical 4]

Embedded image

[Chemical 6] (Here, R5 and R6 are the same as those in the general formula (III).
R7 and R8 are monovalent lower alkyl groups, and Ac 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.

Furthermore, the following formula (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.

[0069]

[Chemical 7] -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 or in the middle of the molecular chain, and the organic group other than hydrogen is selected from the same as 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 rate of these compositions, vinyl group-containing organopolysiloxane such as tetracyclo (methylvinyl) siloxane, carbon-carbon triple bond-containing alcohol,
It is also possible to add a crosslinking inhibitor such as acetone, methyl ethyl ketone, methanol, ethanol or propylene glycol monomethyl ether. These compositions are characterized in that an addition reaction occurs at the time when the three components are mixed and curing begins, but the curing rate rapidly increases 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, and a hydroxyl group-containing organopolysiloxane or a hydrolyzable functional group which is a composition of the condensation type silicone rubber layer may be added. 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.
~ 50g / m2 is preferred, and more preferably 0.5 ~
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.

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 the 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 is free from dust and the like. 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, a method for producing a 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 on the substrate as needed, and the composition was cured 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 is controlled at 50 to 150 ° C. It is formed by heat treatment for minutes to cure the rubber. 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 this exposure step include a high pressure mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, and a fluorescent lamp. After such normal exposure, the plate surface is rubbed with a developing pad or a brush containing a developer described below, the ink repellent layer in the unexposed area is removed and the photosensitive layer is exposed. 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. 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, Astrazone Red, acid dyes and oil-soluble dyes may be added to these developers to dye the image area simultaneously with development. it can.

When developing the waterless planographic printing plate used in this study, for example, 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, it is possible to develop by spraying hot water or steam on the plate surface instead of the above developing solution.

[0089]

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

Synthesis Example 1 Intramolecular epoxidized polybutadiene "Denalex R-4"
5 EPI "(manufactured by Idemitsu Petrochemical Co., Ltd.) 250 g, polyoxypropylene diamine" Dipharmine D-400 "
(Mitsuishi Texaco Chemical Co., Ltd.) 80 g was dropped, and 5
The reaction was carried out at 0 ° C. for 6 hours with stirring to obtain an intramolecular aminated polybutadiene.

This intramolecular aminated polybutadiene 200
g was dissolved in 300 g of tetrahydrofuran, 17 g of glycidyl methacrylate was added dropwise, and the mixture was reacted at 45 ° C. for 5 hours with stirring to obtain a target polymerizable ethylenically unsaturated aminated polybutadiene (polymer 1).

Synthesis Example 2 Intramolecular epoxidized polybutadiene "E-1800-6.
5 g (manufactured by Nippon Petrochemical Co., Ltd., 20 g of pentamethylenediamine) was added dropwise and reacted at 50 ° C. for 5 hours with stirring to obtain an intramolecular aminated polybutadiene.

This intramolecular aminated polybutadiene 200
g was dissolved in 300 g of tetrahydrofuran, 14 g of glycidyl methacrylate was added dropwise, and the mixture was reacted at 45 ° C. for 5 hours with stirring to obtain a target polymerizable ethylenically unsaturated aminated polybutadiene (polymer 2).

Synthesis Example 3 Intramolecular Aminated Polybutadiene "EC-1800-M"
200 g (manufactured by Nippon Petrochemical Co., Ltd.) is dissolved in 300 g of tetrahydrofuran, 19 g of methacrylic acid chloride is added dropwise, and the reaction is carried out while stirring at 40 ° C. for 4 hours to obtain the objective polymerizable ethylenically unsaturated aminated polybutadiene (Polymer 3). ) Got.

Synthetic Example 4 320 g of polybutadiene "Denalex R-45 EPT" (manufactured by Idemitsu Petrochemical Co., Ltd.) having an epoxy group structure at both ends
Hexylamine (18 g) was added dropwise to the mixture and reacted at 50 ° C. for 6 hours with stirring to obtain an intramolecular aminated polybutadiene.

This intramolecular aminated polybutadiene 200
g was dissolved in 300 g of tetrahydrofuran, 17 g of glycidyl methacrylate was added dropwise, and the mixture was reacted at 45 ° C. for 5 hours with stirring to obtain a target polymerizable ethylenically unsaturated aminated polybutadiene (polymer 4).

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

(1) Cancoat 90T-25-3094 (Kansai Paint Co., Ltd., epoxy phenol resin) 15 parts by weight (2) Dimethylformamide 85 parts by weight A photosensitive solution having the following composition was 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) Polymer 1 20 parts by weight (2) Polyurethane of isophorone diisocyanate and polyester polyol consisting of adipic acid and polyethylene glycol 20 parts by weight (3) Tripropylene glycol diglycidyl ether 1 mol and acrylic acid 2 mol Addition reaction product 18 parts by weight (4) N, N'-di- (2-hydroxy-3-methacryloyloxypropyl) -N'-di- (2-hydroxy-3-butoxypropyl) m-xylylenediamine 18 parts by weight Parts (5) 4,4′-bis (diethylamino) benzophenone 5 parts by weight (6) N-methylacridone 8.7 parts by weight (7) crystal violet 0.3 parts by weight (8) ethyl cellosolve 580 parts by weight , Apply a silicone rubber solution having the following composition on this photosensitive layer, 20 ° C., 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 halftone dots 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. The obtained printing plate was attached to an offset printing machine (Komori Sprint 4-color machine) and printed on coated paper using "Dryocolor" indigo ink manufactured by Dainippon Ink and Chemicals, Inc. 150 lines / Prints with very good images were obtained with 2% to 98% halftone dots reproduced.

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. 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 The results are shown in Table 1.

The initial elastic modulus, elongation at break, and 50% stress value of the photosensitive layer were measured by the methods described above. Table 2 shows the results
Shown in

Examples 2 to 4 and Comparative Examples 1 to 2 As shown in Table 1, the type and amount of polybutadiene were changed, and a printing plate precursor was prepared in the same manner as in Example 1.

A gradation positive film having a halftone dot density of 2% to 98% at 175 lines / inch was vacuum adhered to the obtained lithographic printing plate precursor at a vacuum degree of 750 mmHg for 30 seconds, and a 3 Kw ultra-high pressure mercury lamp (Oak Seisakusho) was used. ) Was exposed for 90 seconds from a distance of 1 m. Development was carried out in the same manner as in Example 1 to obtain a waterless planographic printing plate.

The obtained printing plate was attached to an offset printing machine (Komori Sprint 4-color machine) and printed on coated paper using "Dryo Color" indigo ink manufactured by Dainippon Ink and Chemicals, Inc. to reproduce an image. A sex test was conducted.

Further, 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. 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. Printing was performed on woodfree paper at a speed of m and a printing durability test was performed. The results are shown in Table 1.

The initial elastic modulus, elongation at break, and 50% stress value of the photosensitive layer were measured by the methods described above. Table 2 shows the results
Shown in

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

(1) Polyurethane resin (Samplen LQ-SZ18, manufactured by Sanyo Kasei 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) Polymer 2 30 parts by weight (2) Obtained by reacting a polyester polyol of adipic acid with hexane-1,6-diol and 2,2-dimethylpropane-1,3-diol and isophorone diisocyanate Polyurethane 20 parts by weight (3) m-xylylenediamine / glycidyl methacrylate / methyl glycidyl ether = 1/2/2 addition reaction product 18 parts by weight (4) Michler's ketone 3 parts by weight (5) 2,4-diethylthioxanthone 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) ethyl cellosolve 580 parts by weight Subsequently, the following composition is provided on this photosensitive layer. Apply a silicone rubber solution, dry at 110 ° C. for 2 minutes, thickness 1.
A 5 g / m @ 2 silicone rubber layer was provided.

(1) Polyvinyl siloxane with vinyl groups at both ends (number average molecular weight 100,000) 100 parts by weight (2) (CH3) 3SiO (Si (CH3) 2O) 30- (SiH (CH3) O) 10-Si (CH3) 3 3 parts by weight (3) Dibutyltin dilaurate 0.1 parts by weight (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 the 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. The obtained printing plate was attached to an offset printing machine (Komori Sprint 4-color machine) and printed on coated paper using "Dryo Color" indigo ink manufactured by Dainippon Ink and Chemicals, Inc. 150 lines / Prints with very good images were obtained with 2% to 98% halftone dots reproduced.

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 high-quality paper at a speed of m and performing a printing durability test, good printed matter was obtained even after printing 200,000 copies, and the damage to the printing plate after the completion of printing was slight. The results are shown in Table 1.

The initial elastic modulus, elongation at break, and 50% stress value of the photosensitive layer were measured by the methods described above. Table 2 shows the results
Shown in

Examples 6 to 10 and Comparative Example 3 As shown in Table 1, the type and amount of polybutadiene were changed, and a printing plate precursor was prepared in the same manner as in Example 1.

A gradation positive film having a halftone dot of 2% to 98% at 175 lines / inch was vacuum adhered to the obtained lithographic printing plate precursor at a vacuum degree of 750 mmHg for 30 seconds, and a 3 Kw ultra-high pressure mercury lamp (Oak Seisakusho) was used. ) Was exposed for 90 seconds from a distance of 1 m. Development was carried out in the same manner as in Example 1 to obtain a waterless planographic printing plate. The obtained printing plate was attached to an offset printing machine (Komori Sprint 4-color machine), and printed on coated paper using "Dryocolor" indigo ink manufactured by Dainippon Ink and Chemicals, Inc. to perform an image reproducibility test. It was

Further, 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. 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. Printing was performed on woodfree paper at a speed of m and a printing durability test was performed. The results are shown in Table 1.

The initial elastic modulus, elongation at break, and 50% stress value of the photosensitive layer were measured by the methods described above. Table 2 shows the results
Shown in

Example 11 In Example 1, the addition reaction product of 1 mol of tripropylene glycol diglycidyl ether as the component (3) in the photosensitive layer and 2 mol of acrylic acid was added to 1 mol of 1,6-hexanediamine and methacrylic acid. A printing plate precursor was prepared in the same manner as in Example 1 except that the reaction product was changed to 4 mol of acid chloride, and exposure and development were performed in the same manner as in Example 1, and an image reproducibility test and a printing durability test were also performed. All were carried out in the same manner as in Example 1. The results are shown in Table 1.

In the same manner as in Example 1, the initial elastic modulus, elongation at break and 50% stress value of the photosensitive layer were measured. Table 2 shows the results.

Example 12 In Example 1, except that the addition reaction product of 1 mol of tripropylene glycol diglycidyl ether as the component (3) and 2 mol of acrylic acid in the photosensitive layer was changed to tetraethylene glycol diacrylate. A printing plate precursor was prepared in the same manner as in Example 1, exposure and development were also carried out in the same manner as in Example 1, and an image reproducibility test and a printing durability test were also carried out in the same manner as in Example 1. The results are shown in Table 1.

The initial elastic modulus, elongation at break, and 50% stress value of the photosensitive layer were measured in the same manner as in Example 1. Table 2 shows the results.

[0124]

[Table 1]

[Table 2]

[0125]

INDUSTRIAL APPLICABILITY Since the present invention contains an aminated polybutadiene having a polymerizable ethylenically unsaturated group in the photosensitive layer, it is possible to provide a waterless planographic printing plate precursor excellent in printing durability and image reproducibility. it can.

Claims (15)

[Claims] 1. A waterless planographic printing plate precursor in which a photosensitive layer and an ink repellent layer are sequentially laminated on a support, wherein the photosensitive layer contains at least the following components. (1) Aminated butadiene having a polymerizable group (2) Polymer compound other than (1) having film forming ability (3) Photopolymerization initiator 2. The waterless lithographic printing plate precursor as claimed in claim 1, wherein the polymerizable group is an ethylenically unsaturated group. 3. A waterless planographic printing plate precursor according to claim 1, wherein the aminated polybutadiene having a polymerizable group is an intramolecular aminated polybutadiene. 4. The waterless lithographic printing plate precursor according to claim 1, wherein the aminated polybutadiene having a polymerizable group has a number average molecular weight of 500 to 8000. 5. The waterless lithographic printing plate precursor as claimed in claim 1, wherein the photosensitive layer is a photopolymerizable photosensitive layer. 6. The waterless planographic printing plate according to claim 1, wherein the photosensitive layer contains a compound having at least one amino group structure and at least one ethylenically unsaturated bond. Original printing plate. 7. The photosensitive layer contains a compound having at least one amino group structure and at least one ethylenically unsaturated bond and at least one hydroxyl group. A waterless planographic printing plate precursor as described in any of 6 to 6. 8. The photosensitive layer contains a compound having no amino group structure and having at least one ethylenically unsaturated bond.
The waterless planographic printing plate precursor described in any one of. 9. The photosensitive layer contains a compound having no amino group structure, at least one ethylenically unsaturated bond, and at least one hydroxyl group. The waterless planographic printing plate precursor according to any one of claims 1 to 8. 10. The initial elastic modulus of the photosensitive layer after exposure is 5 to 75.
The waterless planographic printing plate precursor as claimed in any one of claims 1 to 9, which has a kgf / mm @ 2. 11. The waterless lithographic printing plate precursor as claimed in claim 1, wherein the breaking elongation of the photosensitive layer after exposure is 100% or more. 12. The 50% stress of the photosensitive layer after exposure is 0.5 to.
3. The pressure is 3.8 kgf / mm @ 2.
11. A waterless planographic printing plate precursor as described in any of 11 to 11. 13. 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. 14. The ink repellent layer comprises a SiH group and —CH═CH.
A waterless planographic printing plate precursor according to any one of claims 1 to 12, which is a silicone rubber layer crosslinked by an addition reaction with a group. 15. A waterless lithographic printing plate obtained by selectively exposing and developing the waterless lithographic printing plate precursor according to claim 1.