JP2003186208A - Method for regenerating lithographic printing plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for regenerating a lithographic printing plate by which an image part is easily and surely removed and contamination by the printing ink during regenerating is further decreased for removing an image so as to regenerate a photographic lithographic printing plate from a lithographic printing plate after printed. <P>SOLUTION: The method for regenerating a lithographic printing plate is carried out by using a photosensitive lithographic printing plate having a photosensitive layer on the surface of an aluminum supporting body and fixed to the plate cylinder of a printing machine. After the photosensitive layer is scanned and exposed by using a laser light source and developed to form an image to prepare a lithographic printing plate, printing ink is supplied to the plate to print the objective material. Then the image is removed by a removing agent to regenerate the aluminum supporting body and a photosensitive layer is again formed on the surface of the aluminum supporting body to regenerate the photosensitive lithographic printing plate. As for the removing agent, an alkaline aqueous solution having ≥10 pH is used. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for recycling a lithographic printing plate, and more specifically, it uses a photosensitive lithographic printing plate having a photosensitive layer formed on the surface of an aluminum support, After printing with the image fixed on the plate cylinder, the image is removed and the aluminum support is regenerated, and the photosensitive layer is re-formed on the surface of the aluminum support to regenerate the photosensitive lithographic printing plate. The present invention relates to a method for reproducing a lithographic printing plate.

[0002]

2. Description of the Related Art In a lithographic printing plate, an image is formed by forming a photosensitive layer on the surface of an aluminum plate as a support to prepare a photosensitive lithographic printing plate and then exposing the photosensitive layer to development processing. This is the printed version. Conventionally, with regard to lithographic printing plates, a technique of removing an image on the surface of an aluminum support and reusing it has been known, and a method of using an acid having a specific composition for removing the image has been known for a long time ( For example, JP-A-50-124706 and JP-A-52-410.
No. 02 and other publications). On the other hand, recently, a method of reproducing a planographic printing plate fixed to a plate cylinder of a printing machine has been proposed (for example, Japanese Patent Laid-Open Nos. 8-52949 and 9-99535). reference).

However, since the photosensitive composition as an image forming material for forming the photosensitive layer of the photosensitive lithographic printing plate contains a substance sensitive to white light, the lithographic printing plate is reproduced on a printing machine. In the latter method, the modification of the photosensitive composition is caused by unintentional exposure in a step other than the exposure step, and it is difficult to sufficiently remove the image from the support surface. However, the re-image formation is not always stable.

By the way, in recent years, with the progress of computer image processing technology, CTP (Computer to Pl) for directly forming an image by laser light without outputting from digital image information to a silver salt mask film.
ate) system is receiving attention. In particular, a CTP system using a high-power semiconductor laser, a YAG laser, a low-power blue-ultraviolet semiconductor laser, or the like, has a shortened plate-making process, is less affected by ambient light during work, and has a plate-making cost. Its practical application is progressing rapidly.

Along with this, in negative-working lithographic printing plates for CTP systems, research on photosensitive compositions for 400-420 nm blue-ultraviolet laser light or laser light in the long wavelength region exceeding 600 nm has recently become active. As a negative photosensitive composition, various photopolymerizable compositions have been proposed. These compositions have the advantage that they can be handled under white or yellow light, because they do not need to contain substances sensitive to white or yellow light.

In the field of lithographic printing plates for CTP systems, infrared laser light is used to form a positive image by increasing the solubility of the exposed area in a developing solution mainly due to changes other than chemical changes. A photosensitive lithographic printing plate having a layer of a photosensitive composition on the surface of a support has also been proposed (for example, JP-A-9-43847 and JP-A-10-104847).
-268512, JP-A-11-84657, JP-A-11-174681, JP-A-11-194504,
(See Japanese Patent Laid-Open No. 11-223936, etc.).

The positive-working lithographic printing plate is a positive-working lithographic printing plate in which a positive image is formed by increasing the solubility of the exposed portion in a developing solution due to a chemical change such as photolysis of an o-quinonediazide compound. Whereas it was formed, the substance that absorbs infrared light such as infrared absorbing dye and converts it into heat and the alkali-soluble resin such as phenol resin are the main photosensitive components, and it is exposed by infrared laser light. It is intended to increase the solubility of the exposed portion in a developing solution by a physical change such as structural transition of the resin due to the generated heat, and it is not necessary to include a substance sensitive to white light such as an o-quinonediazide compound. The advantage is that it can be handled even under white light.

[0008]

[Problems to be Solved by the Invention] However, CTP
In the lithographic printing plate used in the system, when it is regenerated, the above-mentioned photosensitive composition as a photosensitive layer sensitive to a laser beam has an adhesive property to a support of an image formed thereby. It is strong and difficult to remove from the support surface. And, in the reproduction of the planographic printing plate, since the printing ink remains after the printing is completed,
When the image part is peeled off, the printing ink on the image re-attaches to the non-image part of the printing plate, and it remains after the reproduction and stains the non-image part of the printed matter when printing again. It's a problem.

The present invention has been made in view of the above circumstances, and an object of the present invention is to use a photosensitive lithographic printing plate having a photosensitive layer formed on the surface of an aluminum support, in a plate cylinder of a printing machine. After printing with the image formed in a fixed state, the image is removed, the aluminum support is regenerated, the photosensitive layer is re-formed on the surface of the aluminum support, and the photosensitive lithographic printing plate is regenerated. A method of regenerating a lithographic printing plate, which can easily and surely remove an image on an aluminum support and can further reduce stains caused by printing ink when the photosensitive lithographic printing plate is regenerated. To provide a method.

[0010]

In order to solve the above-mentioned problems, a method for recycling a lithographic printing plate according to the present invention comprises a photosensitive layer formed on the surface of an aluminum support and on the plate cylinder of a printing machine. Using the photosensitive lithographic printing plate fixed to, the photosensitive layer is scanned and exposed by a laser light source, developed to expose an image to form a lithographic printing plate, and then a printing ink is supplied to the substrate to be printed. After removing the image with a release agent to regenerate the aluminum support,
In the method of regenerating a lithographic printing plate by forming a photosensitive layer on the surface of an aluminum support and regenerating the photosensitive lithographic printing plate, an alkaline aqueous solution having a pH of 10 or more is used as the release agent.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The reproducing method of the present invention is roughly the method in which a photosensitive layer of a photosensitive lithographic printing plate is subjected to scanning exposure with a laser light source, and development processing is performed to reveal an image to obtain a lithographic printing plate, It is a method of performing printing on a material to be printed, then removing the image, and then forming a photosensitive layer again to regenerate the photosensitive lithographic printing plate, and the photosensitive lithographic printing plate has a surface of an aluminum support. Photosensitive lithographic printing plates are used which are provided with a photosensitive layer on them and which are fixed on a rotatable plate cylinder in various known printing presses.

As the aluminum plate constituting the aluminum support of the lithographic printing plate, aluminum, or silicon, copper, manganese, magnesium, chromium, zinc, lead,
An aluminum alloy containing bismuth, nickel, etc. is used, and its thickness is usually about 0.01 to 10 mm, preferably about 0.05 to 1 mm. Aluminum supports are usually degreased, roughened (grained),
Desmutting treatment, anodizing treatment, sealing treatment, undercoating treatment and the like are performed.

The above-mentioned degreasing treatment is carried out by wiping with a solvent, dipping or steam cleaning, dipping with an alkaline aqueous solution or neutralization with an acid aqueous solution, dipping or spraying with a surfactant. According to the usual method such as the method according to. Further, the roughening treatment is a mechanical treatment method such as a ball polishing method, a brush polishing method, a blast polishing method, a honing polishing method, or a buff polishing method, or
The average roughness Ra defined in JIS B0601 is determined by a conventional method such as an electrolytic etching method and a chemical etching method.
Usually about 0.1 to 1.5 μm, preferably 0.2 to
The thickness is about 1.0 μm. Desmutting treatment may be carried out using acid such as sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, chromic acid, or sodium hydroxide, potassium hydroxide, if necessary.
It is carried out according to a conventional method such as dipping or spraying using an aqueous solution of an alkali such as sodium metasilicate, sodium phosphate, sodium pyrophosphate, potassium phosphate or sodium aluminate.

The anodizing treatment is usually carried out by sulfuric acid alone,
Alternatively, an aqueous solution containing sulfuric acid as a main component, which contains oxalic acid, phosphoric acid, chromic acid, malonic acid, etc. as an electrolytic solution and an aluminum plate as an anode is subjected to electrolytic treatment. The amount of oxide film formed by this is usually 1 to 100 mg / dm ² , and preferably 10 to 50 m.
It is g / dm ² . The sealing treatment is carried out according to a conventional method such as immersion or spraying using boiling water, steam, an aqueous solution of sodium silicate, an aqueous solution of dichromate, etc., if necessary. Further, for the subbing treatment, a resin having a cationic quaternary ammonium salt group, a water-soluble polymer such as polyvinylphosphonic acid, starch, or cellulose, an aqueous solution of a metal salt such as fluorinated zirconic acid, or the like was used, if necessary. It is made according to a conventional method such as dipping or spraying.

In the present invention, the aluminum support is particularly preferably one having a water-soluble polymer thin film layer formed on the surface thereof by an undercoating treatment. Examples of the water-soluble polymer include (meth) acrylic acid (here, “(meth) acrylic” means acrylic and / or methacrylic, and the same applies hereinafter) or an alkali salt thereof. Derivatives of amine salts, etc., itaconic acid or its alkali salts, derivatives of amine salts, etc., 3-vinylpropionic acid or its alkali salts, derivatives of amine salts, etc., vinylsulfonic acid or its alkali salts, derivatives such as amine salts, 2 -Hydroxyethyl (meth) acrylate, 2-
Sulfoethyl (meth) acrylate, polyoxyethylene glycol mono (meth) acrylate, acid phosphooxypolyoxyethylene glycol mono (meth) acrylate, (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethylol (meth) Hydroxyl groups such as acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, allylamine or its halogenated hydroxides, vinyl alcohol, carboxyl groups or salts thereof, sulfonic acid groups or salts thereof, phosphoric acid groups or salts thereof, amide groups , Homopolymers or copolymers of hydrophilic monomers having hydrophilic groups such as amino groups and ether groups, and polysaccharides such as cellulose or its derivatives.

The above water-soluble polymer thin film layer is applied or sprayed as an aqueous solution of the water-soluble polymer on the surface of the aluminum support after the surface treatment, or the aluminum support is immersed in the aqueous solution of the water-soluble polymer. It can be formed by immersing in, and then drying, and the film thickness is usually 10 μm or less.

The above-mentioned aluminum support preferably has a peeling strength of the gum tape pressed on its surface of 500 g / cm or less. In addition, the peeling strength of the gum tape means that the gum tape (“SLION TAPE3” manufactured by SLIONTEC) is attached to the surface of the support at 25 ° C. and 5 kg / cm.
^2. After pressure bonding at 50 cm / min, fix the support on the fixing table, and attach the gum tape from the surface of the support in the direction of 180 degrees for 30
The linear stress (g / cm) obtained by dividing the maximum stress in the 180-degree peeling test of peeling by pulling at a speed of cm / min by the width of the gum tape, and in the present invention, the peel strength is 500 g / cm or less. Is preferable, and is preferably 1 g / cm or more, 10 g / cm
The above is particularly preferable. When the peel strength of the gum tape on the surface of the aluminum support exceeds the above range,
When reproducing the aluminum support, it tends to be difficult to remove the image. On the other hand, when the image size is smaller than the above range,
The printing durability as a lithographic printing plate is poor.

The photosensitive layer formed on the surface of the aluminum support may be either a negative type or a positive type. In the case of the negative type, the photosensitive layer is composed of a photopolymerizable composition containing the following components (A), (B), (C) and (D).

[0019]

[Table 1] (A) Ethylenically unsaturated compound (B) Sensitizer (C) Photopolymerization initiator (D) Polymer binder that absorbs light in the wavelength range of 400 to 1300 nm

The ethylenically unsaturated compound of the component (A) which constitutes the photopolymerizable composition is a photopolymerization initiator of the component (C) described later when the photopolymerizable composition is irradiated with actinic rays. Is a compound having at least one radically polymerizable ethylenically unsaturated bond capable of undergoing addition polymerization by the action of a photopolymerization initiation system containing, and optionally crosslinking and curing.

The above-mentioned ethylenically unsaturated compound includes
A compound having one ethylenically unsaturated bond in the molecule, specifically, for example, (meth) acrylic acid, crotonic acid,
Unsaturated carboxylic acids such as isocrotonic acid, maleic acid, itaconic acid, citraconic acid, and alkyl esters thereof,
(Meth) acrylonitrile, (meth) acrylamide,
Styrene or the like may be used, but from the viewpoint that the polymerizability, the crosslinkability, and the difference in the solubility between the exposed part and the unexposed part in the developing solution can be expanded, an ethylenically unsaturated bond in the molecule can be 2
It is preferable that the compound has one or more, and it is particularly preferable that the unsaturated bond is an acrylate compound derived from a (meth) acryloyloxy group.

Typical examples of the compound having two or more ethylenically unsaturated bonds in the molecule include esters of unsaturated carboxylic acids and polyhydroxy compounds, (meth) acryloyloxy group-containing phosphates, hydroxy ( Urethane (meth) acrylates of (meth) acrylate compound and polyisocyanate compound, and (meth)
Epoxy (meth) acrylates of acrylic acid or a hydroxy (meth) acrylate compound and a polyepoxy compound may, for example, be mentioned.

Specific examples of the above-mentioned esters include unsaturated carboxylic acids such as those mentioned above, and ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, tripropylene glycol, trimethylene glycol, tetra. Methylene glycol, neopentyl glycol, hexamethylene glycol, nonamethylene glycol, trimethylolethane, tetramethylolethane,
Trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol, sorbitol, and their ethylene oxide adducts, propylene oxide adducts, diethanolamine, reaction products with aliphatic polyhydroxy compounds such as triethanolamine, specifically, For example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate,
Tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hexamethylene glycol di (meth ) Acrylate, nonamethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, tetramethylolethane tri (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylol Propane ethylene oxide addition tri (meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, glycerine Lumpur propylene oxide addition tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth)
Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (Meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (meth) acrylate, sorbitol penta (meth) acrylate, sorbitol hexa (meth)
Acrylate and the like, and similar crotonates, isocrotonates, maleates, itaconates, citraconeates and the like.

Further, as the ester thereof, a reaction product of an unsaturated carboxylic acid as described above and an aromatic polyhydroxy compound such as hydroquinone, resorcin, pyrogallol, bisphenol F or bisphenol A, specifically, for example, hydroquinone Di (meth) acrylate, resorcin di (meth) acrylate, pyrogallol tri (meth)
Reaction products of acrylates and the like, unsaturated carboxylic acids as described above, and heterocyclic polyhydroxy compounds such as tris (2-hydroxyethyl) isocyanurate, specifically, for example, tris (2-hydroxyethyl) Isocyanurate di (meth) acrylate, tri (meth) acrylate and the like, and reaction products of unsaturated carboxylic acid, polyvalent carboxylic acid and polyhydroxy compound, specifically, for example, (meth) acrylic acid and phthalate. Condensate of acid and ethylene glycol, condensate of (meth) acrylic acid and maleic acid and diethylene glycol, condensate of (meth) acrylic acid and terephthalic acid and pentaerythritol, (meth) acrylic acid and adipic acid and butane Examples thereof include a condensate of diol and glycerin.

The (meth) acryloyloxy group-containing phosphates are not particularly limited as long as they are phosphate compounds containing a (meth) acryloyloxy group, but among them, the following general formula (Ia) or (I
Those represented by b) are preferred.

[0026]

[Chemical 1]

In the above formulas (Ia) and (Ib), R ⁴² represents a hydrogen atom or a methyl group, n is an integer of 1 to 25,
m is 1, 2 or 3.

It is preferable that n is from 1 to 10, particularly from 1 to 4, and specific examples thereof include (meth) acryloyloxyethyl phosphate, bis [(meth) acryloyloxyethyl] phosphate,
(Meth) acryloyloxyethylene glycol phosphate and the like may be mentioned, and these may be used alone or as a mixture.

Specific examples of the urethane (meth) acrylates include hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycerol di (meth) acrylate, pentaerythritol tri (meth) acrylate. Hydroxy (meth) acrylate compounds such as tetramethylolethane tri (meth) acrylate and hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine methyl ester diisocyanate, lysine methyl ester triisocyanate, dimer acid diisocyanate, 1 , 6,11-Undecatriisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanate-4-isocyanate methyl octa Aliphatic polyisocyanates and the like,
Alicyclic polyisocyanates such as cyclohexane diisocyanate, dimethyl cyclohexane diisocyanate, 4,4′-methylene bis (cyclohexyl isocyanate), isophorone diisocyanate, bicycloheptane triisocyanate, p-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6- Tolylene diisocyanate, xylylene diisocyanate,
Tetramethylxylylene diisocyanate, 4,4'-
Aromatic polyisocyanates such as diphenylmethane diisocyanate, tolidine diisocyanate, 1,5-naphthalene diisocyanate, tris (isocyanatophenylmethane), tris (isocyanatophenyl) thiophosphate, and polyisocyanate compounds such as heterocyclic polyisocyanates such as isocyanurate Examples include reaction products.

Among them, as urethane (meth) acrylates, 4 or more urethane bonds [-NH
-CO-O-] and a compound having 4 or more (meth) acryloyloxy groups are preferable, and the compound is, for example, a compound having 4 or more hydroxyl groups in one molecule such as pentaerythritol and polyglycerin, Compound (i-1) obtained by reacting diisocyanate compound such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, or having two or more hydroxyl groups in one molecule such as ethylene glycol As a compound, "Duranate 24A-100" manufactured by Asahi Kasei Corporation,
Same as "Duranate 22A-75PX", Same as "Duranate 21S-75E", Same as "Duranate 18H-70"
Biuret type such as "B", same "Duranate P-301
-75E ", the same" Duranate E-402-90T ",
Compound (i-2) obtained by reacting a compound having 3 or more isocyanate groups in one molecule such as adduct type such as "Duranate E-405-80T", or isocyanate ethyl (meth) acrylate A compound having 4 or more, preferably 6 or more isocyanate groups in one molecule such as a compound (i-3) obtained by polymerizing or copolymerizing, etc., and specifically, for example, Asahi Kasei "Duranate ME20-100" manufactured by the company (i)
And pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta ( Compounds (i) having one or more hydroxyl groups and two or more, preferably three or more (meth) acryloyloxy groups in one molecule, such as (meth) acrylate.
It can be obtained by reacting with i).

The molecular weight of the above compound (i) is
It is preferably 500 to 200,000, and 1.00
It is particularly preferably from 0 to 150,000. The molecular weight of the urethane (meth) acrylates as described above is
It is preferably 600 to 150,000. Further, it preferably has 6 or more urethane bonds, particularly preferably 8 or more, more preferably 6 or more (meth) acryloyloxy groups, and particularly preferably 8 or more.

Such urethane (meth) acrylates are obtained by, for example, adding the above compound (i) and the above compound (ii) to the former isocyanate group in an organic solvent such as toluene or ethyl acetate. The latter is used at a molar ratio of 1/10 to 10/1 with a catalyst such as n-butyltin dilaurate, if necessary, at 10 to 150 ° C.
It can be manufactured by a method of reacting for 5 minutes to 3 hours.

Among the above urethane (meth) acrylates, those represented by the following general formula (II) are particularly preferable.

[0034]

[Chemical 2]

In the above formula (II), Ra represents a group having a repeating structure of an alkyleneoxy group or an aryleneoxy group and having 4 to 20 oxy groups capable of binding to Rb, and Rb and Rc are each Independently has 1 to 1 carbon atoms
0 represents an alkylene group, Rd represents an organic residue having 1 to 10 (meth) acryloyloxy groups, and Ra, R
b, Rc, and Rd may have a substituent, x is an integer of 4 to 20, y is an integer of 0 to 15, and z is an integer of 1 to 15.

Examples of the repeating structure of the alkyleneoxy group of Ra in the formula (II) include those derived from propylenetriol, glycerin, pentaerythritol and the like, and the repeating structure of the aryleneoxy group is Examples thereof include those derived from pyrogallol, 1,3,5-benzenetriol and the like. The alkylene group of Rb and Rc preferably has independently 1 to 5 carbon atoms, and (meth) in Rd.
The number of acryloyloxy groups is preferably 1 to 7.
Further, x is preferably 4 to 15, y is 1 to 10, and z is preferably 1 to 10, respectively.

Further, as Ra, the following equation (in the equation, k
Is an integer of 2 to 10. ) Is particularly preferred,
Rb and Rc are each independently a dimethylene group,
A monomethyldimethylene group or a trimethylene group is particularly preferable. Further, it is particularly preferable that Rd has the following formula.

[0038]

[Chemical 3]

Specific examples of the above-mentioned epoxy (meth) acrylates include (meth) acrylic acid or the above-mentioned hydroxy (meth) acrylate compound, and (poly) ethylene glycol polyglycidyl ether, ( (Poly) propylene glycol polyglycidyl ether, (poly) tetramethylene glycol polyglycidyl ether, (poly) pentamethylene glycol polyglycidyl ether, (poly) neopentyl glycol polyglycidyl ether, (poly) hexamethylene glycol polyglycidyl ether, (poly ) Aliphatic polyepoxy compounds such as trimethylolpropane polyglycidyl ether, (poly) glycerol polyglycidyl ether, (poly) sorbitol polyglycidyl ether, phenol novo Kkuporiepokishi compounds, brominated phenol novolac polyepoxy compound, (o-,
m-, p-) Cresol novolac polyepoxy compounds, bisphenol A polyepoxy compounds, bisphenol F polyepoxy compounds and other aromatic polyepoxy compounds, sorbitan polyglycidyl ether, triglycidyl isocyanurate, triglycidyl tris (2-hydroxyethyl) Examples include heterocyclic polyepoxy compounds such as isocyanurate, and reaction products with polyepoxy compounds such as.

Other ethylenically unsaturated compounds include, in addition to the above compounds, (meth) acrylamides such as ethylenebis (meth) acrylamide, allyl esters such as diallyl phthalate, and divinylphthalate. Examples include vinyl group-containing compounds. The above ethylenically unsaturated compounds may be used alone or in combination of two or more kinds.

As the ethylenically unsaturated compound as the component (A), ester (meth) acrylates,
(Meth) acryloyloxy group-containing phosphates or urethane (meth) acrylates are preferable,
(Meth) acryloyloxy group-containing phosphates or urethane (meth) acrylates are particularly preferable. The proportion of the (meth) acryloyloxy group-containing phosphates with respect to the whole ethylenically unsaturated compound of the component (A) is preferably 1 to 60% by weight, and 2 to 40% by weight. Is particularly preferable, and the proportion of urethane (meth) acrylates is preferably 0.5 to 50% by weight.
It is particularly preferable that it is ˜40% by weight.

The sensitizer of the component (B) constituting the photopolymerizable composition efficiently absorbs light in the wavelength range of 400 to 1300 nm, and its photoexcitation energy is the photopolymerization of the component (C) described later. A light absorbing dye having a sensitizing function of transmitting to an initiator to decompose the photopolymerization initiator to generate an active radical that induces the polymerization of the ethylenically unsaturated compound as the component (A) is preferable.

These light absorbing dyes include nitrogen atoms,
The basic structure is a structure in which a heteroatom such as an oxygen atom or a sulfur atom is bound by a polymethine (-CH =) _n chain, and typically, the heteroatom forms a heterocycle to form a polymethine chain. A so-called cyanine dye in a broad sense having a structure in which a heterocycle is bonded via, for example, a quinoline dye (so-called cyanine dye in a narrow sense), an indole dye (so-called indocyanine dye), a benzothiazole dye (so-called thiocyanine dye). ), Pyrylium-based, thiopyrylium-based, squarylium-based, croconium-based, azurenium-based, and the like, and so-called polymethine dyes having a structure in which an acyclic heteroatom is bonded via a polymethine chain, and among others, quinoline-based dyes, Cyanine dyes such as indole, benzothiazole, pyrylium, and thiopyrylium dyes, and Methine dyes are preferred.

Among the above cyanine dyes, as the quinoline dye, the following general formula (IIIa),
Those represented by (IIIb) or (IIIc) are preferable.

[0045]

[Chemical 4]

In the above formulas (IIIa), (IIIb) and (IIIc), R ¹ and R ² are each independently an alkyl group which may have a substituent or a substituent. Represents an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, or a phenyl group which may have a substituent, and L ¹ represents tri, penta, which may have a substituent, Hepta, nona or undecamethine group is shown, and two substituents on the penta, hepta, nona or undecamethine group may be linked to each other to form a cycloalkene ring having 5 to 7 carbon atoms, and the quinoline ring is It may have a substituent, in which case two adjacent substituents may be linked to each other to form a condensed benzene ring. Xa ^-
Represents a counter anion.

Here, when R ¹ and R ² in the formulas (IIIa), (IIIb) and (IIIc) are alkyl groups, the number of carbon atoms is usually 1 to 15, preferably 1 to 10, alkenyl group and alkynyl. When it is a group, it usually has 2 to 1 carbon atoms.
5, preferably 2 to 10, and the substituents thereof including the phenyl group include an alkoxy group having a carbon number of usually 1 to 15, preferably 1 to 10, a phenoxy group, a hydroxy group, a phenyl group and the like. Examples of the substituent for L ¹ include alkyl groups having the same number of carbon atoms, amino groups,
Examples of the substituent on the quinoline ring include an alkyl group having the same number of carbon atoms, an alkoxy group having the same number of carbon atoms, a nitro group, and a halogen atom.

As the indole and benzothiazole dyes, those represented by the following general formula (IV) are particularly preferable.

[0049]

[Chemical 5]

In the above formula (IV), Y ¹ and Y ² each independently represent a dialkylmethylene group or a sulfur atom, and R ³ and R ⁴ each independently have a substituent. Optionally an alkyl group, an alkenyl group optionally having a substituent, an alkynyl group optionally having a substituent, or a phenyl group optionally having a substituent, and L ² is
A tri, penta, hepta, nona or undecamethine group which may have a substituent is shown, and two substituents on the penta, hepta, nona or undecamethine group are linked to each other to form a cycloalkene having 5 to 7 carbon atoms. It may form a ring, and the condensed benzene ring may have a substituent. In that case, two adjacent substituents may be linked to each other to form a condensed benzene ring. Xa ^- represents a counter anion.

Here, when R ³ and R ⁴ in the formula (IV) are alkyl groups, the number of carbon atoms is usually 1 to 15, preferably 1 to 10, and when they are alkenyl groups and alkynyl groups, the number of carbon atoms is It is usually 2 to 15, preferably 2 to 10, and the substituents thereof, including the phenyl group, are usually an alkoxy group having 1 to 15, preferably 1 to 10 carbon atoms, a phenoxy group, a hydroxy group, or phenyl. And the like, and examples of the substituent in L ² include an alkyl group having the same number of carbon atoms, an amino group, a halogen atom and the like,
Examples of the substituent on the condensed benzene ring include an alkyl group having the same carbon number as above, an alkoxy group having the same carbon number as above, a nitro group, and a halogen atom.

As the pyrylium-based and thiopyrylium-based dyes, the following general formulas (Va) and (V
Those represented by b) or (Vc) are preferable.

[0053]

[Chemical 6]

The above equations (Va), (Vb) and (Vc)
Wherein Z ¹ and Z ² each independently represent an oxygen atom or a sulfur atom, and R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently
Hydrogen atom or alkyl group, or R ⁵ and R ⁷ and R
⁶ and R ⁸ may be linked to each other to form a cycloalkene ring having 5 or 6 carbon atoms, L ³ represents a mono-, tri-, penta- or heptamethine group which may have a substituent, Two substituents on the tri, penta or heptamethine group may be linked to each other to form a cycloalkene ring having 5 to 7 carbon atoms, and the pyrylium ring and the thiopyrylium ring may have a substituent. In that case, two adjacent substituents may be linked to each other to form a condensed benzene ring. Xa ^- represents a counter anion.

Here, equations (Va), (Vb) and (V
When R ⁵ , R ⁶ , R ⁷ and R ^{8 in} c) are alkyl groups, the number of carbon atoms is usually 1 to 15, preferably 1 to 10,
Examples of the substituent for L ³ include an alkyl group having the same number of carbon atoms, an amino group, a halogen atom and the like, and examples of the substituent for the pyrylium ring and the thiopyrylium ring include aryl groups such as a phenyl group and a naphthyl group.

As the polymethine dye,
What is represented by the following general formula (VI) is preferable.

[0057]

[Chemical 7]

In the above formula (VI), R ⁹ , R ¹⁰ , R ¹¹ and R ¹² each independently represent an alkyl group, and R ¹³ and R
¹⁴ independently represents an aryl group, a furyl group or a thienyl group which may have a substituent, and L ⁴ represents a mono, tri, penta or heptamethine group which may have a substituent. The two substituents on the tri, penta or heptamethine group may be linked to each other to form a cycloalkene ring having 5 to 7 carbon atoms, and the quinone ring and the benzene ring have a substituent. May be. Xa ^- represents a counter anion.

Here, R ⁹ , R ¹⁰ and R ¹¹ in the formula (VI) are
The carbon number of the alkyl group of R ¹² and R ¹² is usually 1 to 15, preferably 1 to 10, and the carbon number when R ¹³ and R ¹⁴ are aryl groups is usually 6 to 20, preferably 6 to 15,
Specific examples of ¹³ and R ¹⁴ include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-furyl group, a 3-furyl group, a 2-thienyl group, and a 3-thienyl group,
As those substituents, ibid alkyl carbon atoms, ibid alkoxy group carbon atoms, a dialkylamino group, hydroxy group, or a halogen atom. Examples of the substituent in L ^4, ibid alkyl group having a carbon number , An amino group, a halogen atom, and the like. Examples of the substituent on the quinone ring and the benzene ring include an alkyl group having the same carbon number as above, an alkoxy group having the same carbon number as above, a nitro group, and a halogen atom.

The above general formulas (IIIa to c),
Examples of the counter anion Xa ⁻ in (IV), (Va to c) and (VI) include Cl ⁻ , Br ⁻ , I ⁻ , ClO.
_{^{4 -, PF 6 -, SbF}} 6 -, AsF 6 -, and, BF ₄ ^-, BC
l ₄ ^- and inorganic acid anions of the inorganic boric acid or the like, such as, benzene sulfonic acid, toluene sulfonic acid, naphthalene sulfonic acid, acetic acid, and methyl, ethyl, propyl, butyl, phenyl, methoxyphenyl, naphthyl, fluorophenyl, difluorophenyl Examples thereof include organic acid anions such as organic boric acid having an organic group such as phenyl, pentafluorophenyl, thienyl and pyrrolyl.

Further, the above general formulas (IIIa to c),
In (IV), (Va-c) and (VI),
By having a barbituric acid anion group or a thiobarbituric acid anion group represented by the following general formula (VIIa) as a substituent on the polymethine chain of L ¹ , L ² , L ³ and L ⁴ , or L ¹ , In the polymethine chain of L ² , L ³ and L ⁴ , a squaric acid anion group or a thiosquaric acid anion group represented by the following general formula (VIIb), or a cyclocon represented by the following general formula (VIIc) An inner salt may be formed by forming an acid anion group or a thiocroconate anion group.

[0062]

[Chemical 8]

The above formulas (VIIa), (VIIb) and
Z in (VIIc)³, Z^Four, Z^Five, Z⁶, Z⁷And Z⁸Is
Each independently represents an oxygen atom or a sulfur atom, R¹⁵as well as
R^{1 6}Each independently have a hydrogen atom and a substituent.
Alkenyl which may be substituted, Alkeni which may have a substituent
Group, an alkoxy group which may have a substituent, or
The phenyl group which may have a substituent is shown.

Here, R ¹⁵ and R ¹⁶ in the formula (VIIa) are
When it is an alkyl group or an alkoxy group, the number of carbon atoms is usually 1 to 15, preferably 1 to 5, and when it is an alkenyl group, the number of carbon atoms is usually 2 to 15, preferably 2 to 5,
It is preferably an alkyl group, and specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group.

The quinoline type represented by the above general formula (IIIa to c), the indole type or benzothiazole type represented by the above general formula (IV), and the above general formula (Va to
Among the pyranium-based or thiopyrylium-based cyanine dyes represented by c) and the polymethine dyes represented by the general formula (VI) above, in the present invention,
The indole-based or benzothiazole-based cyanine dye represented by the above general formula (IV) is particularly preferable.

The quinoline type represented by the above general formulas (IIIa to c), the indole type or benzothiazole type represented by the above general formula (IV), and the quinoline type represented by the above general formulas (Va to c). A cyanine dye such as a pyrylium-based or thiopyrylium-based dye, and the general formula (V
Specific examples of the polymethine dye represented by I) are shown below.

[0067]

[Chemical 9]

[0068]

[Chemical 10]

[0069]

[Chemical 11]

[0070]

[Chemical 12]

[0071]

[Chemical 13]

[0072]

[Chemical 14]

[0073]

[Chemical 15]

[0074]

[Chemical 16]

[0075]

[Chemical 17]

[0076]

[Chemical 18]

[0077]

[Chemical 19]

Examples of the sensitizer include so-called phthalocyanine dyes having a basic structure in which a heterocycle is bound via an azapolymethine chain, and the phthalocyanine dyes are represented by the following general formula ( Those represented by VIII) are preferred.

[0079]

[Chemical 20]

In the above formula (VIII), R ²¹ and R
²² each independently represents an alkoxy group, a thioalkoxy group, an aryloxy group, a thioaryloxy group, an alkylamino group, an arylamino group, a halogen atom, or a hydrogen atom, and M is Zn, Cu, Ni, SnC
l ₂ , AlCl, or a hydrogen atom is shown, and two adjacent substituents on the benzene ring may be linked to each other to form a condensed ring.

Here, R ²¹ and R ²² in the formula (VIII) are
When is an alkoxy group, a thioalkoxy group or an alkylamino group, the carbon number is usually 1 to 10, preferably 1.
And an aryloxy group, a thioaryloxy group, or an arylamino group is a phenoxy group,
Examples thereof include a thiophenoxy group, a phenylamino group, and the like, and M is preferably Zn or SnCl ₂ .

Examples of the sensitizer include dialkylaminobenzene compounds. Among them, dialkylaminobenzophenone compounds, a heterocyclic group is substituted on the carbon atom at the p-position to the amino group on the benzene ring. A dialkylaminobenzene compound having a group is preferable.

As the dialkylaminobenzophenone compound, those represented by the following general formula (IXa) are preferable.

[0084]

[Chemical 21]

In the above formula (IXa), R^{twenty three}, R^{twenty four}, R^{twenty five}
And R²⁶Each independently represents an alkyl group, R²⁷, R
²⁸, R²⁹, And R³⁰Are each independently an alkyl group or
Or hydrogen atom, R^{twenty three}And R^{twenty four}, R^{twenty five}And R²⁶, R^{twenty three}When
R²⁷, R^{twenty four}And R²⁸, R^{twenty five}And R ²⁹, And R²⁶And R
³⁰May independently form a nitrogen-containing heterocycle.
Yes.

Here, R ²³ , R ²⁴ and R in the formula (IXa) are
The carbon number of the alkyl group of ²⁵ and R ²⁶ , and R ²⁷ ,
When R ²⁸ , R ²⁹ and R ³⁰ are alkyl groups, it preferably has 1 to 6 carbon atoms, and when forming a nitrogen-containing heterocycle, it is preferably 5 or 6 membered ring, A 6-membered ring is particularly preferable.

Specific examples of the compound represented by the above general formula (IXa) include, for example, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, and The compound of the structure is mentioned.

[0088]

[Chemical formula 22]

In addition, p is attached to the amino group on the benzene ring.
The heterocyclic group in the dialkylaminobenzene compound having a heterocyclic group as a substituent at the carbon atom at the -position is preferably a 5- or 6-membered ring containing a nitrogen atom, an oxygen atom or a sulfur atom, and a condensed benzene ring A 5-membered ring having is particularly preferable, and as the dialkylaminobenzene compound, a compound represented by the following general formula (IXb) is particularly preferable.

[0090]

[Chemical formula 23]

In the above formula (IXb), R³¹And R³²Is
Each independently represents an alkyl group, R ³³And R³⁴Are each
Independently represent an alkyl group or a hydrogen atom, R³¹When
R³², R ³¹And R³³, And R³²And R³⁴Are each independent
And may form a nitrogen-containing heterocycle. Y³Is oxygen
Atom, sulfur atom, dialkylmethylene group, imino group,
Or an alkylimino group, wherein Y³Contracted to a heterocycle containing
The benzene ring to be combined may have a substituent.

Here, the carbon number of the alkyl group of R ³¹ and R ³² in the formula (IXb) and the carbon number when R ³³ and R ³⁴ are alkyl groups are preferably 1 to 6, When forming a nitrogen-containing heterocycle, it is preferably a 5- or 6-membered ring, and particularly preferably a 6-membered ring. When Y is a dialkylmethylene group, the alkyl group preferably has 1 to 6 carbon atoms, and when Y is an alkylimino group, the alkyl group preferably has 1 to 6 carbon atoms.

Specific examples of the compound represented by the above general formula (IXb) include, for example, 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole and 2- (p. -Dimethylaminophenyl) benzo [4,5] benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,
7] Benzoxazole, 2- (p-dimethylaminophenyl) benzothiazole, 2- (p-diethylaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole , 2- (p-dimethylaminophenyl) -3,3-dimethyl-3H-indole, 2- (p-diethylaminophenyl) -3,3
-Dimethyl-3H-indole and compounds of the following structures:

[0094]

[Chemical formula 24]

Further, other than the compound represented by the above general formula (IXb), as a dialkylaminobenzene compound having a heterocyclic group as a substituent at the carbon atom at the p-position with respect to the amino group on the benzene ring, Is, for example, 2- (p-
Dimethylaminophenyl) pyridine, 2- (p-diethylaminophenyl) pyridine, 2- (p-dimethylaminophenyl) quinoline, 2- (p-diethylaminophenyl) quinoline, 2- (p-dimethylaminophenyl)
Pyrimidine, 2- (p-diethylaminophenyl) pyrimidine, 2,5-bis (p-diethylaminophenyl)
-1,3,4-oxadiazole, 2,5-bis (p-
Diethylaminophenyl) -1,3,4-thiadiazole and the like can be mentioned.

Further, examples of the sensitizer include triphenylmethane leuco dyes such as leuco crystal violet and leucomalachite green disclosed in US Pat. No. 3,479,185, and photoreducible dyes such as erythrosine and eosin Y. U.S. Pat. Nos. 3,549,367 and 3,
Aminophenyl ketones such as Michler's ketone and aminostyryl ketone disclosed in JP-B-652275;
Β-diketones disclosed in U.S. Pat. No. 3,844,790, indanones disclosed in U.S. Pat. No. 4,162,162, JP-A-6-301208, and JP-A-8-1292.
58, JP-A-8-129259, and JP-A-8-146.
Coumarin dyes disclosed in JP-A No. 605 and JP-A-8-212605, ketocoumarin dyes disclosed in JP-A No. 52-112681, and JP-A No. 59-5.
Aminostyrene derivatives and aminophenylbutadiene derivatives disclosed in JP 6403, US Pat. No. 459.
Aminophenyl heterocycles disclosed in US Pat. No. 4,310,684, julolidine heterocycles disclosed in US Pat. No. 4,966,830, JP-A-5-241338, JP-A-7-5685.
And the compounds such as the pyrromethene dyes disclosed in JP-A-10-144242.

The photopolymerization initiator of the component (C) which constitutes the photopolymerizable composition generates active radicals when it is irradiated with light in the coexistence of the above-mentioned sensitizer of the component (B). Radical generators, which are typically halomethylated s-triazine derivatives, halomethylated 1,3,4-oxadiazole derivatives, hexaarylbiimidazole derivatives, titanocene derivatives, organic borate salts, Examples thereof include diaryliodonium salts, carbonyl compounds, and organic peroxides. In the present invention, halomethylated s-triazine derivatives, hexaarylbiimidazole derivatives, and organic borate salts are preferable.

As the halomethylated s-triazine derivative, a derivative in which at least one mono-, di- or trihalogen-substituted methyl group is bonded to the s-triazine ring is preferable, and it is represented by the following general formula (X). Those that are particularly preferable.

[0099]

[Chemical 25]

In the above formula (X), R ³⁵ represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group, and W
Represents an aryl group or a heterocyclic group which may have a substituent, and X represents a halogen atom. r is an integer of 0-2.

Specific examples of the above halomethylated s-triazine derivatives include 2-methyl-4,6-
Bis (trichloromethyl) -s-triazine, 2-n-
Propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl)-
4,6-bis (trichloromethyl) -s-triazine,
2-phenyl-4,6-bis (trichloromethyl) -s
-Triazine, 2- (p-methoxyphenyl) -4,6
-Bis (trichloromethyl) -s-triazine, 2-
(3,4-epoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- [1- (P-Methoxyphenyl) -2,4
-Butadienyl] -4,6-bis (trichloromethyl)
-S-triazine, 2-styryl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s-
Triazine, 2- (p-i-propyloxystyryl)
-4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxynaphthyl) -4,6- Bis (trichloromethyl) -s-triazine, 2- (p-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-ethoxycarbonylnaphthyl) -4,6-bis (trichloro) Methyl) -s-triazine, 2-phenylthio-4,
6-bis (trichloromethyl) -s-triazine, 2-
Benzylthio-4,6-bis (trichloromethyl) -s
-Triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-methoxy-4,6-bis (tribromomethyl) -s-triazine and the like, among which 2- Methyl-4,6-bis (trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloro) Methyl)
-S-triazine, 2- (3,4-epoxyphenyl)
-4,6-bis (trichloromethyl) -s-triazine, 2- [1- (p-methoxyphenyl) -2,4-butadienyl] -4,6-bis (trichloromethyl) -s
-Triazine, 2- (p-methoxystyryl) -4,6
-Bis (trichloromethyl) -s-triazine, 2-
(P-i-propyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine and the like are preferable.

Specific examples of the above halomethylated 1,3,4-oxadiazole derivatives include:
2- (p-methoxyphenyl) -5-trichloromethyl-1,3,4-oxadiazole, 2- (p-methoxystyryl) -5-trichloromethyl-1,3,4-oxadiazole, 2- (O-benzofuryl) -5-trichloromethyl-1,3,4-oxadiazole, 2- [β
Examples include-(o-benzofuryl) vinyl] -5-trichloromethyl-1,3,4-oxadiazole and the like.

Specific examples of the above hexaarylbiimidazole derivatives include 2,2'-bis (o-methoxyphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (p-methoxyphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5,5'- Tetraphenylbiimidazole, 2,2'-bis (o-fluorophenyl) -4,
4 ', 5,5'-tetraphenylbiimidazole, 2,
2'-bis (o-chlorophenyl) -4,4 ', 5
5'-tetra (p-methylphenyl) biimidazole,
2,2'-bis (o-chlorophenyl) -4,4 ',
5,5'-tetra (p-methoxyphenyl) biimidazole, 2,2'-bis (o-chlorophenyl) -4,
4 ', 5,5'-tetra (m, m-dimethoxyphenyl) biimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetra (p-ethoxycarbonylphenyl) Biimidazole, 2,2'-bis (o-bromophenyl) -4,4 ', 5,5'-tetra (p-chloro-p-methoxyphenyl) biimidazole, 2,2'-bis (o-chlorophenyl) ) -4,
4 ', 5,5'-tetra (p-chlorophenyl) biimidazole, 2,2'-bis (o-chlorophenyl)-
4,4 ', 5,5'-Tetra (o, p-dichlorophenyl) biimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetra (p-fluorophenyl) Biimidazole, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (o, p-dibromophenyl) biimidazole, 2,2'-bis (o, p-dichlorophenyl) -4,4 ', 5,5'-
Tetra (o, p-dichlorophenyl) biimidazole,
2,2'-bis (o-bromophenyl) -4,4 ',
5,5'-tetra (o, p-dichlorophenyl) biimidazole, 2,2'-bis (o-bromophenyl)-
4,4 ', 5,5'-Tetra (p-iodophenyl) biimidazole, 2,2'-bis (o-bromophenyl)
-4,4 ', 5,5'-Tetra (o-chloro-p-methoxyphenyl) biimidazole, 2,2'-bis (o-
Chlorophenyl) -4,4 ', 5,5'-tetra (p-
Chloronaphthyl) biimidazole and the like, and among them, a hexaphenylbiimidazole derivative is preferable,
It is preferable that the o-position of the benzene ring bonded to the 2,2'-position on the imidazole ring is substituted with a halogen atom, and the benzene ring at the 4,4 ', 5,5'-position on the imidazole ring is substituted. Are preferably unsubstituted or substituted with a halogen atom or an alkoxycarbonyl group.

Further, as the above titanocene derivatives,
Specifically, for example, dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,4-difluorophenyl), dicyclopentadienyl titanium bis (2, 6-difluorophenyl),
Dicyclopentadienyl titanium bis (2,4,6-
Trifluorophenyl), dicyclopentadienyl titanium bis (2,3,5,6-tetrafluorophenyl), dicyclopentadienyl titanium bis (2,3
3,4,5,6-pentafluorophenyl), di (methylcyclopentadienyl) titanium bis (2,4-difluorophenyl), di (methylcyclopentadienyl) titanium bis (2,6-difluorophenyl) ,
Di (methylcyclopentadienyl) titanium bis (2,4,6-trifluorophenyl), di (methylcyclopentadienyl) titanium bis (2,3,5,6)
-Tetrafluorophenyl), di (methylcyclopentadienyl) titanium bis (2,3,4,5,6-pentafluorophenyl), dicyclopentadienyltitanium bis [2,6-difluoro-3- (1 -Pyrrolyl)
Phenyl] and the like, and among them, derivatives having a dicyclopentadienyl structure and a biphenyl structure are preferable, and those in which the o-position of the biphenyl ring is substituted with a halogen atom are particularly preferable.

Further, as the above-mentioned organic borates, those represented by the following general formula (XI) are particularly preferable.

[0106]

[Chemical formula 26]

In the above formula (XI), R¹⁷, R¹⁸, R¹⁹Over
And R²⁰Are each independently an optionally substituted substituent.
Alkyl group, optionally substituted alkenyl group,
Alkynyl group which may have a substituent, which has a substituent
An aryl group or a heterocyclic group which may be present,
May be linked to each other to form a ring structure,
At least one of them may have a substituent.
It is a rukyll group. Xb ⁺Is a counter cation.

Here, R ¹⁷ , R ¹⁸ and R ¹⁹ in the formula (XI) are
And when R ²⁰ is an alkyl group, the number of carbon atoms is usually 1 to 1.
5, preferably 1 to 5, the number of carbon atoms in the case of an alkenyl group or an alkynyl group is usually 2 to 15, preferably 2 to 5,
When it is an aryl group, the number of carbon atoms is usually 6 to 20, preferably 6 to 15, and when it is a heterocyclic group, the number of carbon atoms is usually 4 to
20, preferably 4 to 15, and examples of the substituents therefor include a halogen atom, an alkyl group, an alkoxy group, a trifluoromethyl group, a trimethylsilyl group and the like.

Specific examples of the organic boron anion of the organic borate represented by the formula (XI) include, for example,
n-butyl-methyl-diphenylboron anion, n-butyl-triphenylboron anion, n-butyl-tris (2,4,6-trimethylphenyl) boron anion, n
-Butyl-tris (p-methoxyphenyl) boron anion, n-butyl-tris (p-fluorophenyl) boron anion, n-butyl-tris (m-fluorophenyl) boron anion, n-butyl-tris (3-fluoro) -4-Methylphenyl) boron anion, n-butyl-tris (2,6-difluorophenyl) boron anion, n
-Butyl-tris (2,4,6-trifluorophenyl) boron anion, n-butyl-tris (2,3,4,
5,6-Pentafluorophenyl) boron anion, n-
Butyl-tris (p-chlorophenyl) boron anion,
Examples thereof include n-butyl-tris (trifluoromethyl) boron anion and n-butyl-tris (2,6-difluoro-3-pyrrolylphenyl) -boron anion.

Examples of the counter cation Xb ⁺ include onium compounds such as alkali metal cations, ammonium cations, phosphonium cations, sulfonium cations and iodonium cations, and pyrylium cations, thiapyrylium cations, indolium cations and the like. Although it can be mentioned, an organic ammonium cation such as tetraalkylammonium is preferable. Further, as a method of allowing the organic borate salt as the photopolymerization initiator of the component (C) to be present in the photopolymerizable composition, a salt of the organic borate anion of the above organic borate salt with a counter cation selected appropriately is used. In addition to the usual method of blending, a method of blending a salt formed by the organic boron anion of the above organic boronic acid salt and the dye cation of the above-mentioned sensitizer of the component (B) can also be adopted.

The polymer binder as the component (D) which constitutes the photopolymerizable composition includes the ethylenically unsaturated compound as the component (A), the sensitizer as the component (B) and the component (C). It has a function as a binder of a photopolymerization initiator and the like, and its polymer binder includes, for example, (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylonitrile, (meth) acrylamide, malein. acid,
Styrene, vinyl acetate, vinylidene chloride, a homo- or copolymer such as maleimide, and polyamide, polyester, polyether, polyurethane, polyvinyl butyral, polyvinyl pyrrolidone, polyethylene oxide, acetyl cellulose, and the like, but among them, alkali developability From the aspect of, a carboxyl group-containing polymer is preferable, and specifically, (meth) acrylic acid and (meth)
An alkyl acrylate (C 1-10) ester or a copolymer further containing styrene as a copolymerization component is preferable, and the acid value of the carboxyl group-containing polymer is 1
It is preferable that the weight average molecular weight is 0 to 250 and the weight average molecular weight is 0.5 to 1,000,000.

Further, as the polymer binder, one having an ethylenically unsaturated bond in the side chain is preferable, and as the ethylenically unsaturated bond, the following general formula (XII
Those represented by a), (XIIb) or (XIIc) are preferred.

[0113]

[Chemical 27]

In the above formulas (XIIa), (XIIb) and (XIIc), R ³⁶ represents a hydrogen atom or a methyl group, and R ³⁷ , R ³⁸ , R ³⁹ , R ⁴⁰ and R ⁴¹ are each independently A hydrogen atom, a halogen atom, an amino group, a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an optionally substituted alkyl group, or a substituted group. Optionally alkoxy group, optionally substituted alkylamino group, optionally substituted alkylsulfonyl group, optionally substituted aryl group, optionally substituted Represents an aryloxy group, an arylamino group which may have a substituent, or an arylsulfonyl group which may have a substituent, and Z ⁹ represents an oxygen atom, a sulfur atom,
Indicates an imino group or an alkylimino group.

Here, an alkyl group for R ^{37 to} R ⁴¹ ,
Examples of the substituent of the alkoxy group, alkylamino group, alkylsulfonyl group, aryl group, aryloxy group, arylamino group, arylsulfonyl group include
Examples thereof include an alkyl group, an alkoxy group, an alkylthio group, an amino group, a dialkylamino group, a nitro group, a cyano group, a phenyl group, and a halogen atom.

The polymer binder having an ethylenically unsaturated bond in the side chain represented by the above formula (XIIa) is a carboxyl group-containing polymer containing allyl glycidyl ether, glycidyl (meth) acrylate and α-ethylglycidyl. (Meth) acrylate, glycidyl crotonate, glycidyl isocrotonate, crotonyl glycidyl ether, itaconic acid monoalkyl monoglycidyl ester,
Aliphatic epoxy group-containing unsaturated compounds such as fumaric acid monoalkyl monoglycidyl ester and maleic acid monoalkyl monoglycidyl ester, or 3,4-epoxycyclohexylmethyl (meth) acrylate, 2,3-
Epoxy cyclopentylmethyl (meth) acrylate,
7,8-Epoxy [tricyclo [5.2.1.0] dec-2-yl] (meth) acrylate, 7,8-epoxy [tricyclo [5.2.1.0] dec-2-yl] oxy An alicyclic epoxy group-containing unsaturated compound such as methyl (meth) acrylate is added at a temperature of about 80 to 120 ° C.
In about 50 hours, 5 to 90 mol% of the carboxyl groups contained in the carboxyl group-containing polymer, preferably 30
It is obtained by reacting about 70 mol%.

The polymer binder having an ethylenically unsaturated bond represented by the above formula (XIIb) in the side chain is allyl (meth) acrylate, 3-allyloxy-2-hydroxypropyl (meth) acrylate, A compound having two or more unsaturated groups such as cinnamyl (meth) acrylate, crotonyl (meth) acrylate, methallyl (meth) acrylate, and N, N-diallyl (meth) acrylamide, and also the above formula (XIIc). Polymer binders having an ethylenically unsaturated bond represented in the side chain are vinyl (meth) acrylate and 1-chlorovinyl (meth).
A compound having two or more kinds of unsaturated groups such as acrylate, 2-phenylvinyl (meth) acrylate, 1-propenyl (meth) acrylate, vinyl crotonate, vinyl (meth) acrylamide, and (meth) acrylic acid, respectively. The ratio of the unsaturated carboxylic acid or the unsaturated carboxylic acid ester of 10 to 90 mol% of the former compound having an unsaturated group, preferably 3
It can be obtained by copolymerizing so that the content of the compound becomes 0 to 80 mol%.

The above-mentioned ethylenically unsaturated compound as the component (A) as the photopolymerizable composition, the above-mentioned sensitizer as the component (B),
The content ratio of each of the photopolymerization initiator as the component (C) and the polymer binder as the component (D) is such that the component (B) is added to 100 parts by weight of the ethylenically unsaturated compound as the component (A). The sensitizer is preferably 0.01 to 20 parts by weight, more preferably 0.05 to 10 parts by weight, and the photopolymerization initiator as the component (C) is preferably 0.1 to 80 parts by weight, further preferably Is 0.5 to 60 parts by weight, the polymer binder of component (D) is preferably 10 to 400 parts by weight, and more preferably 20 to 2 parts by weight.
It is in the range of 00 parts by weight.

In addition to the above components, the photopolymerizable composition may further contain a hydrogen donating compound (E) component for the purpose of improving the photopolymerization initiation ability. Examples of the compound include 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-
Mercaptobenzoxazole, 3-mercapto-1,
2,4-triazole, 2-mercapto-4 (3H)-
Compounds containing mercapto group such as quinazoline, β-mercaptonaphthalene, ethylene glycol dithiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate, hexanedithiol, trimethylolpropane tristhioglyconate, penta Polyfunctional thiol compounds such as erythritol tetrakisthiopropionate, N,
N-dialkylaminobenzoic acid ester, N-phenylglycine, or a salt thereof such as an ammonium salt or a sodium salt thereof, a derivative such as an ester of the same, phenylalanine or a salt thereof such as an ammonium or sodium salt, a derivative of an ester or the like, etc. Examples thereof include amino acids having an aromatic ring or derivatives thereof. Among these, mercapto group-containing compounds, N-phenylglycine, or a salt thereof such as ammonium or sodium salt, or a derivative such as an ester of the same is preferable.

The content ratio of the hydrogen donating compound as the component (E) in the photopolymerizable composition is 0.1 to 5 relative to 100 parts by weight of the ethylenically unsaturated compound as the component (A).
It is preferably 0 part by weight, more preferably 0.5 to 30 parts by weight.

In addition to the above components, the photopolymerizable composition may further contain an amine compound (F) component for the purpose of imparting storage stability to the photopolymerizable composition. , As the amine compound, aliphatic, alicyclic,
Alternatively, it may be any of aromatic amines, and is not limited to monoamines, but may be polyamines such as diamines and triamines, and may be any of primary amines, secondary amines, and tertiary amines. , PKb (dissociation constant) is 7
The following are preferable.

As the amine compound, specifically,
For example, butylamine, dibutylamine, tributylamine, amylamine, diamylamine, triamylamine, hexylamine, dihexylamine, trihexylamine, allylamine, diallylamine, triallylamine, triethanolamine, benzylamine, dibenzylamine, tribenzylamine, etc. , Aliphatic amines which may be substituted with hydroxyl groups or phenyl groups. Of these, tribenzylamine is preferable.

The content of the amine compound as the component (F) in the photopolymerizable composition is 0.1 to 20 parts by weight based on 100 parts by weight of the ethylenically unsaturated compound as the component (A). Is preferable, and more preferably 0.5 to 10 parts by weight.

Further, as the above-mentioned photopolymerizable composition, various additives, for example, a thermal polymerization inhibitor such as hydroquinone, p-methoxyphenol, 2,6-di-t-butyl-p-cresol, 2 parts by weight or less per 100 parts by weight of the ethylenically unsaturated compound as the component A), 20 parts by weight or less of a colorant composed of an organic or inorganic dye or pigment, dioctyl phthalate, didodecyl phthalate, tricresyl phosphate, etc. A plasticizer is also 40 parts by weight or less, a sensitivity property improving agent such as a tertiary amine or a thiol, a coating property improving agent such as a fluorine-based surfactant or a development accelerator is 10 parts by weight or less, and a dye precursor is 30 parts by weight or less. It may be contained at a ratio of not more than parts by weight.

The above-mentioned photopolymerizable composition is usually applied on the surface of the above-mentioned aluminum support as a coating solution prepared by dissolving or dispersing each of the above-mentioned components in a suitable solvent, followed by heating.
By drying, a negative photosensitive lithographic printing plate having a photosensitive layer made of the above photopolymerizable composition formed on the surface of an aluminum support is obtained.

The solvent is not particularly limited as long as it has a sufficient solubility for the components used and gives a good coating property. For example, methyl cellosolve,
Cellosolve solvents such as ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate , Propylene glycol solvents such as dipropylene glycol dimethyl ether, butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, diethyl oxalate, ethyl pyruvate, ethyl-2-hydroxybutyrate, ethyl acetoacetate, methyl lactate, ethyl lactate, Ester solvent such as methyl 3-methoxypropionate, heptanol Hexanol, diacetone alcohol, alcohol solvents such as furfuryl alcohol, cyclohexanone, ketone solvents such as methyl amyl ketone,
Examples thereof include highly polar solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, mixed solvents thereof, and further aromatic hydrocarbons added thereto. The use ratio of the solvent is usually in the range of about 1 to 20 times by weight with respect to the total amount of the photopolymerizable composition.

As the coating method, conventionally known methods such as spin coating, wire bar coating, dip coating, air knife coating, roll coating, blade coating,
And curtain coating can be adopted. The coating amount varies depending on the application, but the dry film thickness is usually 0.3 to 7
μm, preferably 0.5 to 5 μm, particularly preferably 1 to
The range is 3 μm. The drying temperature at that time is, for example, about 60 to 170 ° C, preferably 70 to 150 ° C.
The drying time is, for example, about 5 seconds to 10 minutes, preferably about 10 seconds to 5 minutes.

The negative-working photosensitive lithographic printing plate prevents the photopolymerizable composition from inhibiting polymerization by oxygen on the photosensitive layer of the photopolymerizable composition formed on the surface of the aluminum support as described above. An oxygen barrier layer may be formed.

As a constituent of the oxygen barrier layer,
Water or a water-soluble polymer soluble in a mixed solvent of water and a water-miscible organic solvent such as tetrahydrofuran or an alcohol such as methanol, ethanol, propanol, or isononyl alcohol, and specifically, for example, , Polyvinyl alcohol, and partial acetalization products thereof, cation-modified products thereof with quaternary ammonium salts, etc., and anion-modified products thereof with sodium sulfonate, etc.,
Examples thereof include polypinylpyrrolidone, polyethylene oxide, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and the like.

Among them, polyvinyl alcohol and its derivatives are preferable from the viewpoint of oxygen barrier property, and
It is preferable that the saponification degree is 70 mol% or more, further 80 mol% or more, and the weight average molecular weight is 0.2 to 500,000, further 0.4 to 100,000.

The oxygen barrier layer contains polyvinyl alcohol and its derivative in an amount of 30% by weight.
It is preferably at least above, more preferably 40 to 100% by weight. From the viewpoint of adhesion to the photosensitive layer, vinylpyrrolidone-based polymers such as polyvinylpyrrolidone and vinylpyrrolidone-vinyl acetate copolymer, acrylic polymer emulsions, diisocyanate compounds, p
-Toluenesulfonic acid, hydroxyacetic acid, etc. are preferably contained, among them, a vinylpyrrolidone-based polymer is preferable, and further, the content ratio of the vinylpyrrolidone-based polymer is 0.1 to 70% by weight. Preferably 5-6
It is more preferably 0% by weight.

Furthermore, the oxygen barrier layer preferably contains an organic acid such as succinic acid and an organic acid salt such as ethylenediaminetetraacetic acid from the viewpoint of imparting storage stability, and polyoxyethylene alkylphenyl. Nonionic properties such as ether, anionic properties such as sodium dodecylbenzene sulfonate, cationic properties such as alkyltrimethylammonium chloride, antifoaming agents, dyes, plasticizers, pH adjusting agents, etc. may be contained. , Their total content is preferably 10% by weight or less,
It is more preferably 5% by weight or less.

The above oxygen barrier layer is formed as a solution of water or a mixed solvent of water and a water-miscible organic solvent by the same coating method as that for the above-mentioned photosensitive layer, and its coating amount is a dry film thickness. The range of 1 to 10 g / m ² is preferable, and the range of 1.5 to 7 g / m ² is more preferable.

In the present invention, when the photosensitive layer formed on the surface of the aluminum support is a negative type, the photosensitive layer is a positive type photosensitive layer containing the following components (A) and (B). It is composed of a composition.

[0135]

[Table 2] (A) Photothermal conversion substance that absorbs light from an image exposure light source and converts it into heat (B) Alkali-soluble resin

The photothermal conversion substance of the component (A) is not particularly limited as long as it is a compound capable of absorbing the light of the image exposure light source and converting it into heat, but the wavelength range 600 to 1300.
Examples include organic or inorganic dyes and pigments, organic dyes, metals, metal oxides, metal carbides, metal borides, and the like, which have an absorption band in part or all of the nm range. Among them, the light absorbing dye is particularly effective. These light-absorbing dyes efficiently absorb light in the above wavelength range, but hardly absorb light in the ultraviolet region, or are substantially insensitive to light absorption, and are not sensitive to white light. It is a compound that does not act to modify the photosensitive composition depending on weak ultraviolet rays.

As the above-mentioned light absorbing dye, similar to the above-mentioned light absorbing dye, a structure in which a hetero atom such as a nitrogen atom, an oxygen atom or a sulfur atom is bonded by a polymethine (-CH =) _n chain is referred to as a basic structure. Typically, a so-called broadly defined cyanine dye having a structure in which the heteroatom forms a heterocycle and the heterocycle is bonded via a polymethine chain, specifically, for example, a quinoline ( So-called narrow sense cyanine system), indole system (so-called indocyanine system),
Examples include benzothiazole-based (so-called thiocyanine-based), pyrylium-based, thiopyrylium-based, squarylium-based, croconium-based, azurenium-based, and so-called polymethine dyes having a structure in which an acyclic heteroatom is bonded via a polymethine chain. Among them, quinoline,
Cyanine dyes such as indole dyes, benzothiazole dyes, pyrylium dyes, and thiopyrylium dyes, and polymethine dyes are preferable.

In addition, diiminium dyes, phthalocyanine dyes and the like are also mentioned as typical ones.
Of these, diiminium dyes are preferable.

Of the above cyanine dyes, the quinoline dyes are preferably those represented by the following general formula (Ia), (Ib) or (Ic), as in the above dyes.

[0140]

[Chemical 28]

The above formulas (Ia), (Ib) and (Ic)
Wherein R ¹ and R ² are each independently an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, Alternatively, it represents a phenyl group which may have a substituent, and L ¹
Is an optionally substituted tri, penta, hepta,
Nona or undecamethine group is shown, and two substituents on the penta, hepta, nona or undecamethine group may be linked to each other to form a cycloalkene ring having 5 to 7 carbon atoms, and the quinoline ring is a substituent group. In that case, two adjacent substituents may be bonded to each other to form a condensed benzene ring. X ⁻ represents a counter anion. ]

Here, the formulas (Ia), (Ib), and (I
When R ¹ and R ^{2 in} c) are alkyl groups, the number of carbon atoms is usually 1 to 15, preferably 1 to 10, and when they are alkenyl groups and alkynyl groups, the number of carbon atoms is usually 2 to 15, preferably 2 10 to 10, and the substituents thereof, including the phenyl group, usually have 1 to 15 carbon atoms, preferably 1 to 1 carbon atoms.
Examples thereof include an alkoxy group of 0, a phenoxy group, a hydroxy group, and a phenyl group. Examples of the substituent of L ¹ include an alkyl group having the same number of carbon atoms, an amino group, a halogen atom, and the like, and a substituent of the quinoline ring. Examples thereof include an alkyl group having the same carbon number as above, an alkoxy group having the same carbon number as above, a nitro group, and a halogen atom.

As the indole-based and benzothiazole-based dyes, those represented by the following general formula (II) are particularly preferable as in the above-mentioned dyes.

[0144]

[Chemical 29]

In the above formula (II), Y ¹ and Y ² each independently represent a dialkylmethylene group or a sulfur atom, and R ³ and R ⁴ each independently have a substituent. Optionally an alkyl group, an alkenyl group optionally having a substituent, an alkynyl group optionally having a substituent, or a phenyl group optionally having a substituent, and L ² is
A tri, penta, hepta, nona or undecamethine group which may have a substituent is shown, and two substituents on the penta, hepta, nona or undecamethine group are linked to each other to form a cycloalkene having 5 to 7 carbon atoms. It may form a ring, and the condensed benzene ring may have a substituent. In that case, two adjacent substituents may be linked to each other to form a condensed benzene ring. X ⁻ represents a counter anion.

Here, when R ³ and R ⁴ in the formula (II) are alkyl groups, the number of carbon atoms is usually 1 to 15, preferably 1 to 10, and when they are alkenyl groups and alkynyl groups, the number of carbon atoms is It is usually 2 to 15, preferably 2 to 10, and the substituents thereof, including the phenyl group, are usually an alkoxy group having 1 to 15, preferably 1 to 10 carbon atoms, a phenoxy group, a hydroxy group, or phenyl. And the like, and examples of the substituent in L ² include an alkyl group having the same number of carbon atoms, an amino group, a halogen atom and the like,
Examples of the substituent on the condensed benzene ring include an alkyl group having the same carbon number as above, an alkoxy group having the same carbon number as above, a nitro group, and a halogen atom.

As the pyrylium-based and thiopyrylium-based dyes, those represented by the following general formula (IIIa), (IIIb), or (IIIc) are particularly preferable as in the above-mentioned dyes.

[0148]

[Chemical 30]

In the above formulas (IIIa), (IIIb) and (IIIc), Z ¹ and Z ² each independently represents an oxygen atom or a sulfur atom, and R ⁵ , R ⁶ , R ⁷ and R ⁸ is
Each independently, a hydrogen atom or an alkyl group, or
R ⁵ and R ⁷ and R ⁶ and R ⁸ are linked to each other and have 5 or 6 carbon atoms.
Which may form a cycloalkene ring, and L ³ represents an optionally substituted mono, tri, penta or heptamethine group, and the two substituents on the tri, penta or heptamethine group are They may be linked to each other to form a cycloalkene ring having 5 to 7 carbon atoms, and the pyrylium ring and the thiopyrylium ring may have a substituent, in which case two adjacent substituents are linked to each other. To form a condensed benzene ring. X ⁻ represents a counter anion.

Here, the formulas (IIIa), (IIIb),
And R in (IIIc)^Five, R⁶, R ⁷And R⁸Is alkyl
The number of carbon atoms in the group is usually 1 to 15, preferably 1 to
10 and L³As the substituent in, the same as above
The alkyl group, amino group or halogen atom of
In the pyrylium and thiopyrylium rings.
Examples of the substituent include aryl groups such as phenyl group and naphthyl group.
And so on.

As the polymethine dyes, those represented by the following general formula (IV) are particularly preferable as in the above-mentioned dyes.

[0152]

[Chemical 31]

In the above formula (IV), R ⁹ , R ¹⁰ , R ¹¹ and R ¹² each independently represent an alkyl group, and R ¹³ and R
¹⁴ independently represents an aryl group, a furyl group or a thienyl group which may have a substituent, and L ⁴ represents a mono, tri, penta or heptamethine group which may have a substituent. The two substituents on the tri, penta or heptamethine group may be linked to each other to form a cycloalkene ring having 5 to 7 carbon atoms, and the quinone ring and the benzene ring have a substituent. May be. X ⁻ represents a counter anion.

Here, R ⁹ , R ¹⁰ and R ¹¹ in the formula (IV) are
The carbon number of the alkyl group of R ¹² and R ¹² is usually 1 to 15, preferably 1 to 10, and the carbon number when R ¹³ and R ¹⁴ are aryl groups is usually 6 to 20, preferably 6 to 15,
Specific examples of ¹³ and R ¹⁴ include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-furyl group, a 3-furyl group, a 2-thienyl group, and a 3-thienyl group,
As those substituents, ibid alkyl carbon atoms, ibid alkoxy group carbon atoms, a dialkylamino group, hydroxy group, or a halogen atom. Examples of the substituent in L ^4, ibid alkyl group having a carbon number , An amino group, a halogen atom, and the like. Examples of the substituent on the quinone ring and the benzene ring include an alkyl group having the same carbon number as above, an alkoxy group having the same carbon number as above, a nitro group, and a halogen atom.

Further, as the diiminium dye, those having at least one N, N-diaryliminium salt skeleton and represented by the following general formula (Va) or (Vb) are particularly preferable.

[0156]

[Chemical 32]

In the above formulas (Va) and (Vb), R ¹⁵ ,
R ¹⁶ , R ¹⁷ and R ¹⁸ each independently have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent. An optionally substituted alkynyl group or an optionally substituted alkoxy group, and R ¹⁹ and R ²⁰ each independently represent an optionally substituted alkyl group or a substituent. An alkenyl group which may have, an alkynyl group which may have a substituent, an alkoxy group which may have a substituent, an acyloxy group which may have a substituent, or a substituent It represents a phenyl group which may have, and the benzene ring and iminoquinone ring may have a substituent. X ⁻ represents a counter anion. The electronic bond (dotted line) in the formula (Vb) shows a resonance state with other electronic bonds.

Here, R in the formulas (Va) and (Vb)
¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹And R ²⁰Is an alkyl group,
When it is a lucoxy group, it usually has 1 to 15 carbon atoms, preferably
When it is 1 to 10, an alkenyl group or an alkynyl group
Has usually 2 to 15 carbon atoms, preferably 2 to 10 carbon atoms,
As a substituent in them, alkyl having the same carbon number as above is used.
Group, same as above, alkoxy group having carbon number, carboxy group, acyl
Oxy group, alkoxycarbonyl group, hydroxy group,
Mino group, alkylamino group, halogenated alkyl group,
Or a halogen atom.
The substituent on the minoquinone ring is the same as the above carbon number.
Alkyl group, same as above carbon number alkoxy group, acyl group, nit
And a halogen atom or the like.

Among the above-mentioned diiminium dyes, R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ in the above general formulas (Va) and (Vb) are alkyl groups, and R ¹⁹ and R ²⁰ are also alkyl groups. It is particularly preferable that R ¹⁹ and R ²⁰ are phenyl groups having a dialkylamino group as a substituent.

The above general formulas (Ia to c) and (I
Examples of the counter anion X ⁻ in I), (IIIa to c), (IV) and (Va to b) include Cl ⁻ and B.
Inorganic acid anions such as r ⁻ , I ⁻ , ClO ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , AsF ₆ ⁻ , and BF ₄ ⁻ , BCl ₄ ^{−, and the} like, and benzenesulfonic acid, toluenesulfonic acid , Naphthalene sulfonic acid, acetic acid, and organic acid anions such as methyl, ethyl, propyl, butyl, phenyl, methoxyphenyl, naphthyl, fluorophenyl, difluorophenyl, pentafluorophenyl, thienyl, and pyrrolyl-containing organic groups. Can be mentioned.

The above general formulas (Ia to c) and (I
In I), (IIIa-c) and (IV),
By having a barbituric acid anion group or a thiobarbituric acid anion group represented by the following general formula (VI) as a substituent on the polymethine chain of L ¹ , L ² , L ³ and L ⁴ , or L ¹ , In the polymethine chain of L ² , L ³ and L ⁴ , the squaric acid anion group or thiosquaric acid anion group represented by the following general formula (VII), or the cyclocone represented by the following general formula (VIII) An inner salt may be formed by forming an acid anion group or a thiocroconate anion group.

[0162]

[Chemical 33]

The above formulas (VI), (VII), and (V
In III), Z ³ , Z ⁴ , Z ⁵ , Z ⁶ , Z ⁷ and Z ⁸ each independently represent an oxygen atom or a sulfur atom, and R ¹⁵ and R ¹⁶
Are each independently a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkoxy group which may have a substituent, or a substituent. The phenyl group which may have is shown.

Here, when R ²¹ and R ²² in the formula (VI) are an alkyl group or an alkoxy group, the number of carbon atoms is usually 1 to
15, preferably 1 to 5, the number of carbon atoms in the case of an alkenyl group is usually 2 to 15, preferably 2 to 5, but is preferably an alkyl group, and as the alkyl group,
Specifically, a methyl group, an ethyl group, a propyl group, a butyl group, or the like can be given.

The quinoline type represented by the above general formulas (Ia to c), the indole type or benzothiazole type represented by the above general formula (IV), and the above general formulas (IIIa to
c) a pyranium-based or thiopyrylium-based cyanine dye, a polymethine dye represented by the general formula (IV), and the general formula (Va to
Among the polymethine dyes represented by b) in the present invention, the indole-based or benzothiazole-based cyanine dyes represented by the general formula (II) are particularly preferable.

The quinoline type represented by the above general formulas (Ia to c), the indole type or benzothiazole type represented by the above general formula (II), and the above general formula (II
Cyanine dyes represented by Ia to c) such as pyrylium or thiopyrylium, and the above general formula (I)
Specific examples of the polymethine dye represented by V) and the diiminium dye represented by the above general formulas (Va to b) are shown below.

[0167]

[Chemical 34]

[0168]

[Chemical 35]

[0169]

[Chemical 36]

[0170]

[Chemical 37]

[0171]

[Chemical 38]

[0172]

[Chemical Formula 39]

[0173]

[Chemical 40]

[0174]

[Chemical 41]

[0175]

[Chemical 42]

[0176]

[Chemical 43]

[0177]

[Chemical 44]

[0178]

[Chemical formula 45]

In the present invention, the content ratio of the photothermal conversion substance of the component (A) in the positive photosensitive composition is 0.
It is preferably 5 to 30% by weight, more preferably 1 to 20% by weight, and particularly preferably 2 to 10% by weight.

As the alkali-soluble resin as the component (B), a resin having a phenolic hydroxyl group, specifically, a phenol resin such as a novolac resin or a resole resin, a polyvinylphenol resin, or a phenolic hydroxyl group is used. Acrylic acid derivative copolymers and the like are preferable, and among these, phenol resins such as novolac resins and resole resins or polyvinylphenol resins are preferable, phenol resins are more preferable, and novolac resins are particularly preferable.

The novolac resin is, for example, phenol,
o-cresol, m-cresol, p-cresol,
2,5-xylenol, 3,5-xylenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, propylphenol, n-butylphenol, t-butylphenol, 1-naphthol, 2-naphthol, 4,4 '. At least one of phenols such as biphenyldiol, bisphenol-A, pyrocatechol, resorcinol, hydroquinone, pyrogallol, 1,2,4-benzenetriol and phloroglucinol under acid catalysis, for example, formaldehyde, acetaldehyde, propione Aldehydes such as aldehyde, benzaldehyde and furfural (paraformaldehyde may be used in place of formaldehyde and paraaldehyde in place of acetaldehyde), or acetone, methyl ether. A resin obtained by polycondensation with at least one kind of ketones such as chill ketone and methyl isobutyl ketone. Among them, in the present invention, phenol as phenols, o-cresol, m-cresol, p-cresol, and 2 , 5-xylenol, 3,5
-Polycondensates of xylenol, resorcinol and formaldehyde, acetaldehyde, propionaldehyde as aldehydes or ketones are preferred.

In particular, m-cresol: p-cresol:
The mixing ratio of 2,5-xylenol: 3,5-xylenol: resorcinol is 40 to 100: 0 to 5 in molar ratio.
A mixed phenol of 0: 0 to 20: 0 to 20: 0 to 20 or a mixing ratio of phenol: m-cresol: p-cresol in a molar ratio of 1 to 100: 0 to 7: 0.
A polycondensate of 60 mixed phenols and formaldehyde is preferable, and the photosensitive composition may contain a dissolution inhibitor as described later. In that case, m-cresol: p-cresol: 2. 5-xylenol: 3,5
-Mixing ratio of xylenol: resorcinol is 70 to 100: 0 to 30: 0 to 20: 0 to 20: 0 to 2 in molar ratio.
0 mixed phenols or a mixing ratio of phenol: m-cresol: p-cresol in a molar ratio of 10 to 1
A polycondensate of mixed phenols of 00:00 to 60: 0 to 40 and formaldehyde is preferable.

The novolak resin preferably has a polystyrene-reduced weight average molecular weight (MW) of 1,000 to 15,000 as measured by gel permeation chromatography, and more preferably 1,500 to 10,000.

Further, the resole resin is a resin polycondensed in the same manner except that an alkali catalyst is used instead of the acid catalyst in the polycondensation of the novolak resin, and the same phenols as those in the above novolak resin and a mixture thereof are used. The composition and aldehydes or ketones are preferable, and those having similar weight average molecular weight (MW) are also preferable.

The polyvinylphenol resin is, for example, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, dihydroxystyrene,
Trihydroxystyrene, tetrahydroxystyrene,
Hydroxystyrenes such as pentahydroxystyrene, 2- (o-hydroxyphenyl) propylene, 2- (m-hydroxyphenyl) propylene, and 2- (p-hydroxyphenyl) propylene (these are chlorine, bromine in the benzene ring). , Or a halogen atom such as iodine or fluorine, or an alkyl group having 1 to 4 carbon atoms as a substituent.) In the presence of a radical polymerization initiator or a cationic polymerization initiator. Polymers of hydroxystyrenes which may have an alkyl group having 1 to 4 carbon atoms as a substituent on the benzene ring are preferable among the resins polymerized with. Polymers of styrenes are preferred. The weight average molecular weight (MW) is preferably 1,000 to 100,000, more preferably 1,500 to 50,000.

The content ratio of the alkali-soluble resin as the component (B) in the positive photosensitive composition is preferably 50 to 99% by weight, more preferably 60 to 98% by weight, and 70 to 97. It is particularly preferred that it is% by weight.

The positive type photosensitive composition containing the photothermal conversion substance as the component (A) and the alkali-soluble resin as the component (B) has a solubility in the alkali developing solution in the exposed and unexposed areas. For the purpose of increasing the difference, a dissolution inhibitor which is not decomposed by light in the infrared region may be contained.

Examples of the above-mentioned dissolution inhibitors are sulfonic acid esters, phosphoric acid esters and aromatic carboxylic acid esters described in detail in JP-A Nos. 10-268512 and 11-288089. JP-A-11-190903, compounds, aromatic disulfones, carboxylic acid anhydrides, aromatic ketones, aromatic aldehydes, aromatic amines, aromatic ethers, compounds having a triarylmethane skeleton, etc. Acid-coloring dyes having a lactone skeleton, an N, N-diarylamide skeleton, and a diarylmethylimino skeleton described in detail in JP-A-11-143076, and a lactone skeleton and a thiolactone. Examples thereof include base coloring dyes having a skeleton and a sulfolactone skeleton.

Further, as a dissolution inhibitor, for example, polyethylene glycols, polyethylene glycol polypropylene glycol block copolymers, polyethylene glycol alkyl ethers, polyethylene glycol polypropylene glycol alkyl ethers, polyethylene glycol alkyl phenyl ethers, polyethylene glycol fatty acid esters , Polyethylene glycol alkyl amines, polyethylene glycol alkyl amino ethers, glycerin fatty acid ester and its polyethylene oxide adducts, sorbitan fatty acid ester and its polyethylene oxide adduct, sorbit fatty acid ester and its polyethylene oxide adduct, pentaerythritol Fatty acid ester and its polyethylene Oxide adducts, nonionic surfactants such as polyglycerol fatty acid esters.

The content ratio of the above dissolution inhibitor in the positive photosensitive composition is preferably 50% by weight or less, more preferably 0.01 to 30% by weight,
It is particularly preferably 0.1 to 20% by weight.

The positive type photosensitive composition containing the photothermal conversion substance as the component (A) and the alkali-soluble resin as the component (B) is used for the purpose of improving developability such as imparting underdeveloping property. , Preferably an organic acid having a pKa of 2 or more and an anhydride of the organic acid may be contained.

As the above-mentioned organic acid and its anhydride,
For example, JP-A-60-88942 and JP-A-63-27.
Those described in JP-A-6048, JP-A-2-96754 and the like are used. Specifically, glyceric acid,
Methylmalonic acid, dimethylmalonic acid, propylmalonic acid, succinic acid, malic acid, mesotartaric acid, glutaric acid, β
-Methyl glutaric acid, β, β-dimethyl glutaric acid, β
-Ethyl glutaric acid, β, β-diethyl glutaric acid, β
-Aliphatic saturated carboxylic acids such as propyl glutaric acid, β, β-methyl propyl glutaric acid, pimelic acid, suberic acid and sebacic acid, and aliphatic unsaturated carboxylic acids such as maleic acid, fumaric acid and glutaconic acid, 1,1 -Cyclobutanedicarboxylic acid, 1,3-cyclobutanedicarboxylic acid,
1,1-cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,1-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3
-Carbocyclic saturated carboxylic acids such as cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, 1,2
-Cyclohexene dicarboxylic acid, 2,3-dihydroxybenzoic acid, 3,4-dimethylbenzoic acid, 3,4-dimethoxybenzoic acid, 3,5-dimethoxybenzoic acid, p-toluic acid, 2-hydroxy-p-toluic acid , 2-hydroxy-m-toluic acid, 2-hydroxy-o-toluic acid, mandelic acid, gallic acid, phthalic acid, isophthalic acid,
Carbocyclic unsaturated carboxylic acids such as terephthalic acid, and anhydrides such as Meldrum's acid, ascorbic acid, succinic anhydride, glutaric anhydride, maleic anhydride, cyclohexenedicarboxylic anhydride, cyclohexanedicarboxylic anhydride, phthalic anhydride Things can be mentioned.

The content of the above organic acid or its anhydride in the positive photosensitive composition is preferably 30% by weight or less, more preferably 20% by weight or less, and 10% by weight or less. Is particularly preferable.

Further, the positive type photosensitive composition containing the photothermal conversion substance as the component (A) and the alkali-soluble resin as the component (B) includes, for example, Victoria Pure Blue (4
2595), Crystal Violet (42555),
Crystal violet lactone, auramine O (41
000), Catillon Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170), Safranine OK 70: 100 (5
0240), Erioglaucine X (42080), Fast Black HB (26150), No. 120 / Rionol Yellow (21090), Rionol Yellow GRO (21090), Shimla First Yellow 8
GF (21105), Benzidine Yellow 4T-564
D (21095), Shimla Fast Red 4015
(12355), Lionol Red B4401 (158
50), Fastgen Blue TGR-L (7416)
0), a coloring agent such as a pigment or a dye such as Lionol Blue SM (26150) may be contained. The numbers in parentheses above refer to the color index (CI).

The content of the above colorant in the positive photosensitive composition is preferably 50% by weight or less,
More preferably 0.5 to 30% by weight, 2 to 20
It is particularly preferred that it is% by weight.

Further, the positive type photosensitive composition containing the photothermal conversion substance as the component (A) and the alkali-soluble resin as the component (B) is exposed to light when the alkali-soluble resin is the phenol resin. And a crosslinking agent having a function of crosslinking the phenol resin may be contained for the purpose of imparting chemical resistance, printing durability, etc. to the positive image by crosslinking the resin by post-heating after development. , As the cross-linking agent, typically, a methylol group as a functional group,
Examples thereof include an alkoxymethyl group obtained by modifying it with alcohol, and an amino compound having at least two acetoxymethyl groups. Specifically, melamine derivatives such as methoxymethylated melamine (Cymel 300 series (1) manufactured by Mitsui Cytec Co., Ltd.), benzoguanamine derivative (methyl / ethyl mixed alkoxylated benzoguanamine resin (Cymel 11 manufactured by Mitsui Cytec Co., Ltd.
00 series (2) and the like), glycoluril derivatives (tetramethylol glycoluril resin (CYMEL 1100 series (3) and the like manufactured by Mitsui Cytec Co., Ltd.)), urea resin derivatives, and resole resins.

The content of the above crosslinking agent in the positive photosensitive composition is preferably 20% by weight or less.
It is more preferably 0% by weight or less, and particularly preferably 5% by weight or less.

Further, in the positive type photosensitive composition containing the photothermal conversion substance as the component (A) and the alkali-soluble resin as the component (B), a positive type photosensitive composition is used for the purpose of improving sensitivity and developing property. An ionic, nonionic or amphoteric surfactant may be contained.

For example, as the anionic surfactant,
Sodium lauryl sulphate (Emar 0), higher alcohol sodium sulphate (Emal 40 paste), triethanolamine lauryl sulphate (Emal TD), ammonium lauryl sulphate (Emal AD 25R), sodium dodecylbenzene sulphonate (Neoberex N)
o. 25) and the like fatty acid salts, alkyl sulfate ester salts, and alkylbenzene sulfonates.

As the anionic surfactant, sodium alkylnaphthalene sulfonate (Belex NB.L), sodium dialkylsulfosuccinate (Belex OT.P), sodium alkyldiphenyl ether disulphonate (Belex SS.L), Alkylphosphoric acid potassium salt (electrostripper F), polyoxyethylene lauryl ether sodium sulfate (Emar 20C), polyoxyethylene alkyl ether sulfate triethanolamine (Emar 20T), polyoxyethylene alkyl allyl ether (Lebenol W)
Examples thereof include alkylnaphthalene sulfonates such as Z), alkyl sulfosuccinates, and alkyl diphenyl ether disulphonates. Further, as anionic surfactants, sodium salt of β-naltarensulphonic acid formalin condensate (Demol N), sodium salt of special aromatic sulfonic acid formalin condensate (Demol M
S), naltarensulphonic acid formalin condensate such as special polycarboxylic acid type polymer surfactant (Demole EP), and special polycarboxylic acid type polymer surfactant.

As the nonionic surfactant, polyoxyethylene lauryl ether (Emulgen 104P),
Polyoxyethylene cetyl ether (Emulgen 210
P), polyoxyethylene stearyl ether (Emulgen 306P), polyoxyethylene oleyl ether, polyoxyethylene higher alcohol ether, polyoxyethylene noelphenyl ether (Emulgen 9
03) and other polyoxyethylene alkyl ethers and polyoxyethylene alkyl allyl ethers.
Further, as nonionic surfactants, polyoxyethylene derivatives (Emulgen A-60), sorbitan monolaurate (Reodol SP / L10), sorbitan monolaurate (Reodol Super SP / L10), sorbitan disparate Examples thereof include polyoxyethylene derivatives such as (Emazole S.20), oxyethylene / oxypropylene block copolymers, and sorbitan fatty acid esters.

Further, as the nonionic surfactant, polyoxyethylene sorbitan such as polyoxyethylene sorbitan monolaurate (Reodol TW-L120), polyoxyethylene sorbit tetraoleate (Reodol 430) and glycerol monostearate. Examples thereof include fatty acid ester, polyoxyethylene sorbitol fatty acid ester, and glycerin fatty acid ester. Further, other nonionic surfactants include polyethylene glycol monolaurate (Emanone 111).
2), polyoxyethylene alkylamine (Amate 1
05), alkyl alkanolamides (Aminone PK
-02S) and other polyoxyethylene fatty acid esters, polyoxyethylene alkylamines, and alkylalkanolamines.

Examples of the amphoteric surfactant include alkyl betaines such as lauryl betaine (Amphitol 24B) and lauryl carboxymethyl hydroxyethyl imidazolinium betaine (Amphitol 20Y). The names in parentheses of the above-mentioned respective surfactants are the product names in the case of Kao Corporation.

The content of the above surfactant in the positive photosensitive composition is preferably 0.001 to 5% by weight, more preferably 0.002 to 3% by weight, and 0.005% by weight. It is particularly preferred that it is ˜1% by weight.

In addition to the above-mentioned components, the positive-working photosensitive composition also contains, for example, a coating composition improving agent, an adhesion improving agent, a sensitivity improving agent, a sensitizing agent, a developing property improving agent and the like. Various additives usually used in the product may further be contained in the range of 20% by weight or less, preferably 10% by weight or less.

The positive photosensitive composition does not contain a compound sensitive to light in the ultraviolet region, such as an onium salt, a diazonium salt or a quinonediazide group-containing compound,
It is substantially insensitive to light in the ultraviolet region. Here, “having substantially no sensitivity to light in the ultraviolet region” means that there is no substantial difference in solubility in an alkali developer before and after irradiation with light having a wavelength of 360 to 450 nm, It means that it does not have an image forming ability in a general sense.

In forming the photosensitive layer on the surface of the aluminum support, the above-mentioned positive-working photosensitive composition is usually used as a solution or dispersion of the above components dissolved in a suitable solvent. After being applied to the body surface, it is heated and dried.

The above-mentioned solvent is not particularly limited as long as it has a sufficient solubility for the components used and gives a good coating property, and examples thereof include methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate and ethyl. Cellosolve solvents such as cellosolve acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether, etc. Glycol solvent, butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, diethyl oxalate,
Ester-based solvents such as ethyl pyruvate, ethyl-2-hydroxybutyrate, ethyl acetoacetate, methyl lactate, ethyl lactate, and methyl 3-methoxypropionate, alcohol-based solvents such as heptanol, hexanol, diacetone alcohol, and furfuryl alcohol. , Cyclohexanone, ketone type solvents such as methyl amyl ketone,
Examples thereof include highly polar solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, mixed solvents thereof, and further aromatic hydrocarbons added thereto. The proportion of the solvent used is usually in the range of about 1 to 20 times by weight with respect to the total amount of the photosensitive composition.

As the coating method, conventionally known methods such as spin coating, wire bar coating, dip coating, air knife coating, roll coating, blade coating, and curtain coating can be used. The coating amount varies depending on the application, but the dry film thickness is usually 0.3 to 7 μm,
Preferably 0.5-5 μm, particularly preferably 1-3 μm
The range is. The drying temperature at that time is, for example,
About 60 to 170 ° C, preferably about 70 to 150 ° C,
The drying time is, for example, about 5 seconds to 10 minutes, preferably about 10 seconds to 5 minutes.

In the present invention, in the state where the negative or positive type photosensitive lithographic printing plate as described above is fixed on the plate cylinder of a printing machine, the photosensitive layer is subjected to scanning exposure by a laser light source and developed. Then, the image is exposed to form a lithographic printing plate, and then printing ink is supplied in accordance with a conventional method to perform printing on an object to be printed.

As the laser light source for exposure, for example, HeNe laser, argon ion laser, YA
G laser, HeCd laser, semiconductor laser, ruby laser and the like can be mentioned, but particularly in the wavelength range of 400 to 4
A light source that emits laser light in the blue-ultraviolet region of 20 nm or a light source that emits laser light in the near-infrared region of wavelength range 600 to 1300 nm is preferable. Such a light source is not particularly limited, but specifically, an indium gallium nitride semiconductor laser that oscillates 410 nm in the former wavelength range and 8 in the latter wavelength range is used.
Examples thereof include a semiconductor laser that oscillates 30 nm and a YAG laser that oscillates 1064 nm.

The scanning exposure method is not particularly limited, and examples thereof include a flat surface scanning exposure method, an outer surface drum scanning exposure method, and an inner surface drum scanning exposure method. The output light intensity of the laser is usually 1 to 100 mW, preferably 3 to 70 mW in the former wavelength range, and usually 0.1 to 100 W, preferably 0.5 to 70 W in the latter wavelength range. Is usually 2 to 30 μm, and preferably 4 to 20 μm for both the former wavelength region and the latter wavelength region. The scanning speed is usually 50 to 500 m / sec, preferably 100 to 400 m / sec in the former wavelength region, and usually 0.1 to 500 m / sec, preferably 0.3 to in the latter wavelength region. 40
The laser exposure amount on the photosensitive layer in the scanning exposure is usually 1 to 10 in the former wavelength range.
In the latter wavelength range, it is usually 1 to 20 so that it becomes 0 μJ / cm ² or less, preferably 5 to 50 μJ / cm ² or less.
It is set to 0 mJ / cm ² or less, preferably 5 to 150 J / cm ² or less.

The development treatment after exposure is usually carried out using a developing solution, and examples of such a developing solution include sodium silicate, potassium silicate, lithium silicate, ammonium silicate, sodium metasilicate and potassium metasilicate. , Sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium diphosphate, sodium triphosphate, ammonium diphosphate, ammonium triphosphate, sodium borate, potassium borate, boric acid Inorganic alkali salts such as ammonium, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, monobutylamine, monoethanolamine, diethanolamine, triethanone Amine, monoisopropanolamine, alkaline developing solution comprising an aqueous solution of about 0.1 to 5% by weight of an organic amine compound diisopropanolamine or the like is used. Among them, silicates of alkali metals such as inorganic silicates such as sodium silicate and potassium silicate are preferable.

[0214] The developing solution contains polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters from the viewpoint that the range of developing conditions can be stably widened. , Nonionics such as monoglyceride alkyl esters, anionic properties such as alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, sulfosuccinate ester salts, and amphoteric properties such as alkyl betaines and amino acids Surfactants, water-soluble organic solvents such as isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like can be added. The pH of the developer is preferably 9-14.

The above-mentioned development treatment is usually carried out by a known development method such as spraying a photosensitive lithographic printing plate with the above-mentioned developing solution or the like, preferably about 10 to 50 ° C., more preferably 15
The temperature is about 45 ° C. and the time is about 5 seconds to 10 minutes. At that time, the oxygen blocking layer may be removed in advance with water or the like, or may be removed at the time of development.

As another developing method, for example, as described in JP-A No. 11-10827, the above-mentioned alkaline developer or the above-mentioned surfactant or water-soluble organic solvent added thereto, Alternatively, a so-called permeation development method in which the solution or the like is permeated into the photosensitive layer after exposure as a penetrant, and a physical stimulus is applied as necessary to peel off the non-exposed portion from the surface of the support to develop.
Alternatively, as described in JP-A-10-333321, a photosensitive lithographic printing plate is mounted on a plate cylinder of a printing machine,
A so-called printing method in which printing ink is supplied onto the photosensitive layer, and the above-mentioned ink is transferred to the blanket cylinder together with the non-exposed area by utilizing the adhesive force of the ink to separate the non-exposed area from the surface of the support and develop. A developing method or the like can also be adopted.

After printing with the planographic printing plate on which an image has been formed by the above-mentioned development processing, the image portion is removed and the printing plate is reproduced. In such regeneration, the image is removed by a release agent and the aluminum support is regenerated. In the present invention, as a release agent for removing an image, p
It is important to use an alkaline aqueous solution of H10 or higher, preferably pH 11-14. PH value of release agent is 1
When it is less than 0, the peeling of the photosensitive layer is insufficient and the residue of the photosensitive layer is liable to occur, and a difference in hydrophilicity occurs between the non-image portion and the image portion of the support surface after peeling, Image density unevenness is likely to occur on the printed matter.

The above-mentioned stripping agent is an aqueous solution containing at least an alkaline agent, preferably an aqueous solution containing a nonionic, anionic or amphoteric surfactant in addition to the alkaline agent, more preferably an alkaline agent. , An aqueous solution containing a water-soluble organic solvent in addition to the surfactant. The above-mentioned alkaline agent greatly contributes to the peeling of the photosensitive image, and the surfactant and the water-soluble organic solvent have the functions of swelling the photosensitive layer and allowing the alkaline agent to penetrate into the photosensitive layer.

Examples of the alkaline agent used in the release agent include sodium silicate, potassium silicate, lithium silicate, ammonium silicate, sodium metasilicate, potassium metasilicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, carbonic acid. Sodium, sodium bicarbonate, potassium carbonate, dibasic sodium phosphate, sodium triphosphate,
Inorganic alkali salts such as dibasic ammonium phosphate, tribasic ammonium phosphate, sodium borate, potassium borate, ammonium borate, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylammon, monoisopropylamine, diisopropylamine, monobutylamine, Monoethanolamine,
Usually 0.01 to 20% by weight, preferably 0.1 to 10% by weight, more preferably 0.1 to 5% by weight, of an organic amine compound such as diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine and the like.
An alkaline developer comprising an aqueous solution of is used. Of these, organic amine compounds such as triethanolamine and diethanolamine are preferable.

Examples of the surfactant in the stripping solution include various anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants. For example, as anionic surfactant, sodium lauryl sulfate (Emar 0), higher alcohol sodium sulfate (Emal 40 paste), triethanolamine lauryl sulfate (Emal TD), ammonium lauryl sulfate (Emal AD / 25R), dodecylbenzene Examples thereof include fatty acid salts such as sodium sulfonate (Neoberex No. 25), alkyl sulfate ester salts, and alkylbenzene sulfonates.

As the anionic surfactant, sodium alkylnaphthalene sulfonate (Belex NB.L), sodium dialkylsulfosuccinate (Belex OT.P), sodium alkyldiphenyl ether disulphonate (Belex SS.L), Alkylphosphoric acid potassium salt (electrostripper F), polyoxyethylene lauryl ether sodium sulfate (Emar 20C), polyoxyethylene alkyl ether sulfate triethanolamine (Emar 20T), polyoxyethylene alkyl allyl ether (Lebenol W)
Examples thereof include alkylnaphthalene sulfonates such as Z), alkyl sulfosuccinates, and alkyl diphenyl ether disulphonates. Further, as anionic surfactants, sodium salt of β-naltarensulphonic acid formalin condensate (Demol N), sodium salt of special aromatic sulfonic acid formalin condensate (Demol M
S), naltarensulphonic acid formalin condensate such as special polycarboxylic acid type polymer surfactant (Demole EP), and special polycarboxylic acid type polymer surfactant.

As the nonionic surfactant, polyoxyethylene lauryl ether (Emulgen 104P),
Polyoxyethylene cetyl ether (Emulgen 210
P), polyoxyethylene stearyl ether (Emulgen 306P), polyoxyethylene oleyl ether, polyoxyethylene higher alcohol ether, polyoxyethylene noelphenyl ether (Emulgen 9
03) and other polyoxyethylene alkyl ethers and polyoxyethylene alkyl allyl ethers.
Further, as nonionic surfactants, polyoxyethylene derivatives (Emulgen A-60), sorbitan monolaurate (Reodol SP / L10), sorbitan monolaurate (Reodol Super SP / L10), sorbitan disparate Examples thereof include polyoxyethylene derivatives such as (Emazole S.20), oxyethylene / oxypropylene block copolymers, and sorbitan fatty acid esters.

Further, as nonionic surfactants, polyoxyethylene sorbitan such as polyoxyethylene sorbitan monolaurate (Reodol TW-L120), polyoxyethylene sorbit tetraoleate (Reodol 430) and glycerol monostearate. Examples thereof include fatty acid ester, polyoxyethylene sorbitol fatty acid ester, and glycerin fatty acid ester. Further, other nonionic surfactants include polyethylene glycol monolaurate (Emanone 111).
2), polyoxyethylene alkylamine (Amate 1
05), alkyl alkanolamides (Aminone PK
-02S) and other polyoxyethylene fatty acid esters, polyoxyethylene alkylamines, and alkylalkanolamines.

As cationic surfactants and amphoteric surfactants, stearylamine acetate (acetamine 86),
Lauryl trimethyl ammonium chloride (coatamine 24P), cetyl trimethyl ammonium chloride (coatamine 60W), distearyl dimethyl ammonium chloride (coatamine D86R), alkylbenzyl dimethyl ammonium chloride (samisol C), lauryl retain (amphetol 24B), lauryl dimethylamine oxide (Amphithor 20
N), alkyl amines such as lauryl carboxymethyl hydroxyethyl imidazolinium betaine (Amphitol 20Y), quaternary ammonium salts, alkyl betaines and amine oxides. The names in parentheses of the above-mentioned respective surfactants are the product names in the case of Kao Corporation.

As the water-soluble organic solvent in the stripping solution, a water-soluble organic solvent such as isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol or diacetone alcohol can be added. . The blending amount of the above surface active agent and the water-soluble organic solvent is usually 0.01 to
It is 50% by weight, preferably 0.1 to 20% by weight, more preferably 0.1 to 10% by weight.

The peeling step is usually carried out by a known method such as immersing the photosensitive lithographic printing plate in the above-mentioned peeling liquid or applying the above-mentioned peeling liquid to the photosensitive lithographic printing plate, and usually, preferably 10 to 50 ° C, more preferably 15 to 45
It is performed at a temperature of about ℃ for a time of about 5 seconds to 10 minutes.

As another peeling method, the above-mentioned alkaline developer, or the above-mentioned surfactant or water-soluble organic solvent or the like added thereto, or a solution thereof is used as a penetrating agent to obtain a photosensitive material after printing. This is done by permeating the layers and applying physical stimuli as needed.

In the present invention, after the image is removed with the release agent to regenerate the aluminum support as described above, a photosensitive layer is again formed on the surface of the aluminum support to regenerate the photosensitive lithographic printing plate. . In the present invention, by using an alkaline aqueous solution having a specific pH value as a release agent when removing the image portion after printing, the image portion can be easily and surely removed, and the image portion of the planographic printing plate can be removed. Since the printing ink remaining on the top can be prevented from reattaching to the non-image area during the peeling process, and the hydrophilicity of the non-image area can be maintained, the printing ink stains more when the photosensitive lithographic printing plate is regenerated. It can be reduced. Therefore, according to the present invention, it is possible to obtain a high-quality printed matter without causing stains due to ink adhesion on the non-image area even when printing with a regenerated planographic printing plate.

[0229]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.

Example 1: Aluminum plate (thickness 0.2 m
m) was defatted with a 3% by weight aqueous sodium hydroxide solution,
25 ° C in a hydrochloric acid bath of 18 g / liter, 80 A / dm
Electrolytically etch at a current density of ² for 15 seconds, then
Desmut treatment is performed with a 1% by weight sodium hydroxide aqueous solution at 50 ° C for 5 seconds and then with a 10% by weight hydrochloric acid aqueous solution at 25 ° C.
Neutralize for 2 seconds, wash with water, then in a 30 wt% sulfuric acid bath at 30 ° C,
Anodizing treatment was performed at a current density of 10 A / dm ² for 16 seconds, followed by washing with water and drying to obtain an oxide film amount of 21 mg / d.
An m ² aluminum support was obtained.

The gum tape peeling strength of the surface of the obtained aluminum support was measured by the following method, and was 30
It was 0 g / cm. The gum tape peeling strength was measured under the above conditions.

Subsequently, the photopolymerizable composition was applied to the surface of the obtained aluminum support by a bar coater and dried to form a photosensitive layer. The photopolymerizable composition as a coating liquid is an ethylenically unsaturated compound of the following component (A),
(B) component sensitizing dye, (C) component photopolymerization initiator,
The polymer binder as the component (D) and other components were mixed in 1090 parts by weight of cyclohexanone at room temperature to prepare a solution. The dry film thickness after coating was 2 g / m ² . Then, using a bar coater, a mixed aqueous solution of polyvinyl alcohol and polyvinylpyrrolidone (polyvinyl alcohol: polyvinylpyrrolidone = 95) is formed on the formed photosensitive layer.
(Wt%: 5 wt%) was applied so that the dry film thickness would be 3 g / m ^2, and dried to form an oxygen barrier layer, whereby a negative photosensitive lithographic printing plate was prepared.

[0233]

[Table 3] (A) Ethylenically unsaturated compound The following compound (A-1); 25 parts by weight The following compound (A-2); 5 parts by weight The following compound (A-3); 25 parts by weight

[0234]

[Chemical formula 46]

[0235]

[Table 4] (B) Sensitizer The following compound (B-1); 2 parts by weight

[0236]

[Chemical 47]

[0237]

[Table 5] (C) Photoinitiator 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine (C-1); 5 parts by weight (D) Polymer binder methyl A reaction product obtained by reacting a methacrylate (80 mol%) / methacrylic acid (20 mol%) copolymer with 3,4-epoxycyclohexylmethyl acrylate (60 mol% of the carboxyl groups of the methacrylic acid component).
Reaction, acid value 60, weight average molecular weight 75,000) (D-
1); 45 parts by weight Other components Pigment (ethyl violet); 5 parts by weight

Then, an exposure device (“Trend Setter” manufactured by Creo Co., Ltd.) using a semiconductor laser having a wavelength of 830 nm as a light source was applied to the obtained negative-type photosensitive lithographic printing plate.
3244T ") was used for scanning exposure with various exposure energies. And 0.8% by weight of sodium carbonate and anionic surfactant ("Perex NBL" manufactured by Kao Co.)
The negative type lithographic printing plate on which the scanning line image was formed was obtained by immersing the film in a developing solution containing a 3% by weight aqueous solution at 25 ° C. for 30 seconds and then washing with water. The sensitivity obtained from the minimum exposure energy for forming a scanning line image is 100 mJ / cm ^2.
Met.

Printing was carried out using the negative type lithographic printing plate which was exposed with the minimum exposure energy and developed as described above. In the printing process, after the above negative type lithographic printing plate was detachably fixed to the plate cylinder of a lithographic printing machine (“Diamond F-2” manufactured by Mitsubishi Heavy Industries, Ltd.), the negative type lithographic printing plate was wetted. The dampening water supply mechanism supplies dampening water ("Astro No. 1 Mark II" manufactured by Nikken Chemical Co., Ltd.), and the printing ink supply mechanism supplies "printing ink (" High Echo Magenta "manufactured by Toyo Ink Co., Ltd.). Printing of 10,000 sheets was performed.

After the printing is completed, in a state where the planographic printing plate is fixed to the plate cylinder, the printing ink on the plate surface is washed and removed, and then, by a roller of an image removing mechanism attached to the printing machine,
A release agent for removing the image was applied on the plate surface. As a release agent, 10% by weight of aluminum hydroxide particles were added and dispersed, and a negative type lithographic printing plate developing solution triethanolamine 5% by weight, benzyl alcohol 0.1% by weight, phenoxyethanol 5% by weight, anionic surfactant were used. A 6% by weight aqueous solution of the agent sodium dibutylnaphthalene sulfonate was used. Then, after rubbing the image surface with a brush,
The aluminum support was regenerated by wiping with gauze to remove the image and washing with water.

Subsequently, the surface of the regenerated aluminum support was again coated with a coating liquid as a photopolymerizable composition similar to the above by a roller of a coating liquid coating mechanism for the photopolymerizable composition attached to a printing machine. Then, the negative type photosensitive lithographic printing plate was prepared by heating and drying to form a photosensitive layer. Then, again, using the exposure mechanism, after scanning and exposing the above-mentioned photosensitive layer with laser light, using the roller of the developing mechanism attached to the printing machine, in the same manner as described above for the photosensitive layer. By developing, a negative image was revealed to prepare a negative lithographic printing plate. The sensitivity at that time was determined as the minimum exposure energy for forming a scanning line image, and was 100 mJ / cm ² as before reproduction.
Met.

Then, using the above negative type lithographic printing plate exposed and developed with an exposure energy of 100 mJ / cm ² , the second printing was carried out in the same manner as above.
High quality prints were obtained at 30,000 prints. Further, in the same manner, the lithographic printing plate after the second printing was repeatedly reproduced and printed, and the plate was reproduced 10 times. The sensitivity at that time was 100 mJ, which was the same as before the reproduction.
/ Cm ² , and high-quality printed matter was obtained after printing 1000 sheets using the printing plate. The degree of residual line image after the aluminum support was regenerated at that time was evaluated by visual observation according to the following ranks, and was A rank.

[0243]

[Table 6] A: The residual rate of the line image is less than 1%. B: Residual rate of line image is 1% or more and less than 10%. C: Line image residual rate is 10% or more and less than 70%. D: Residual rate of line image is 70% or more.

Regarding the negative photosensitive lithographic printing plate prepared by using the regenerated aluminum support, a white fluorescent lamp (36W white fluorescent lamp "Neolmi Super FLR40S-W / M / 36" manufactured by Mitsubishi Electric Corporation) was used. After irradiating with the light of (4) at a light intensity of 400 lux for 10 minutes, the same developing treatment as above was carried out. As a result, the photosensitive layer was completely dissolved and removed, and the safelight property under a white lamp was good. It was confirmed that there is.

Example 2: Same as Example 1 except that after anodic oxidation treatment, it was immersed in a 50 ppm carboxymethylcellulose aqueous solution for 5 seconds and dried to form a hydrophilic polymer thin film layer having a film thickness of 0.01 μm on the surface. To prepare an aluminum support, and then by the same method as in Example 1,
The photopolymerizable composition was applied to the surface of the aluminum support and dried to form a photosensitive layer, to prepare a negative photosensitive lithographic printing plate. The photopolymerizable composition as a coating liquid for forming the photosensitive layer was prepared by stirring the following components (A) to (D) and other components in 1090 parts by weight of cyclohexanone at room temperature. The gum tape peeling strength of the surface when the aluminum support was produced was 300 g / cm, and
Unlike Example 1, an oxygen barrier layer was not formed on the surface of the photosensitive layer.

[0246]

[Table 7] (A) Ethylenically unsaturated compound The following compound (A-6); 11 parts by weight The following compound (A-7): 24 parts by weight

[0247]

[Chemical 48]

[0248]

[Table 8] (B) Sensitizer Compound (B-1) above; 2 parts by weight (C) Photopolymerization initiator Compound (C-1) above; 5 parts by weight (D) Polymer binder vinyl methacrylate (40 mol%) / methacrylic acid (15 mol%) / acrylonitrile (15 mol%) /
(3-allylglycidyloxy-2-hydroxy-propyl) -oxymethacrylate (30 mol%) or copolymer (weight average molecular weight 200,000) (D-3); 45 parts by weight (F) amine compound tribenzylamine ( F-1); 5 parts by weight Other components Pigment (ethyl violet); 5 parts by weight

Then, the negative photosensitive lithographic printing plate was exposed by the same process as in Example 1 to prepare a negative lithographic printing plate, and then a printing process was performed. The sensitivity of the negative photosensitive lithographic printing plate was 150 mJ / cm ² . The degree of residual line image after the aluminum support was regenerated after printing was rank A. Further, in the same manner as in Example 1, a reproduction / printing was repeated 9 times, and then a negative type lithographic printing plate was prepared using an aluminum support which was reproduced 10 times, and the sensitivity was 150 mJ / cm ² which was the same as before reproduction. Then, printing was carried out using the negative type lithographic printing plate which was exposed with the exposure energy of 150 mJ / cm ² and developed, and a high-quality printed matter was obtained after printing 10,000 sheets. . The negative photosensitive lithographic printing plate prepared by using the recycled aluminum support at that time had a good safelight property under a white light.

Example 3: An aluminum plate support similar to that of Example 1 was prepared, and then the polymer binder of the photopolymerizable composition applied to the surface of the aluminum support was changed to the following component (D). A photosensitive layer was formed in the same manner as in Example 2 to prepare a negative photosensitive lithographic printing plate.

[0251]

[Table 9] (D) Polymer binder Methyl methacrylate (50 mol%) / isobutyl methacrylate (30 mol%) / methacrylic acid (20 mol%) copolymer was reacted with 3,4-epoxycyclohexylmethyl acrylate. The reaction product obtained by the reaction (50 mol% of the carboxyl groups of the methacrylic acid component react)
(D-4); 25 parts by weight of styrene (63 mol%) / acrylic acid (37 mol%) copolymer, a reaction product obtained by reacting 3,4-epoxycyclohexyl methyl acrylate (acrylic acid component 50% by mole of the carboxyl groups of
5); 25 parts by weight

Then, the negative photosensitive lithographic printing plate was exposed by the same process as in Example 1 to prepare a negative lithographic printing plate, and then a printing process was performed. The sensitivity of the negative-working photosensitive lithographic printing plate was 120 mJ / cm ² , and the degree of residual line image after reproduction of the aluminum support after printing was rank A. Further, in the same manner as in Example 1, a reproduction / printing was repeated 9 times, and then a negative type lithographic printing plate was prepared using an aluminum support which was reproduced 10 times, and the sensitivity was 120 mJ / cm ² which was the same as before reproduction. Then, printing was performed using the negative type lithographic printing plate which was exposed and developed with the exposure energy of 120 mJ / cm ² , and a high-quality printed matter was obtained after printing 10,000 sheets. . The negative photosensitive lithographic printing plate prepared by using the recycled aluminum support at that time had a good safelight property under a white light.

Example 4 A negative-working photosensitive lithographic printing plate was prepared in the same manner as in Example 1 except that the photopolymerizable composition as a coating liquid for forming the photosensitive layer was changed. The coating liquid was prepared by adding the following components (A) to (D) and other components to propylene glycol monomethyl ether acetate 400.
One part by weight was mixed with 740 parts by weight of cyclohexanone at room temperature to prepare a solution.

[0254]

Table 10 (A) Ethylenically unsaturated compound Compound (A-1); 22 parts by weight Compound (A-6): 11 parts by weight Compound (A-7): 22 parts by weight (B) ) Sensitizer 4,4′-bis (diethylamino) benzophenone (B
-3); 9 parts by weight (C) photopolymerization initiator 2,2'-bis (o-chlorophenyl) -4,4 ',
5,5'-tetraphenylbiimidazole (C-3);
15 parts by weight (D) Polymer binder methyl methacrylate (80 mol%) / methacrylic acid (20 mol%) copolymer was reacted with 3,4-epoxycyclohexyl methyl acrylate to obtain a reaction product (methacryl 50 mol% of the carboxyl group of the acid component
Reaction, acid value 53, weight average molecular weight 70,000) (D-6);
45 parts by weight (E) Hydrogen donating compound 2-mercaptobenzothiazole (E-1); 5 parts by weight N-phenylglycine benzyl ester (E-2); 5
Parts by weight (F) amine compound tribenzylamine (F-1); 3 parts by weight other components pigment (copper phthalocyanine); 4 parts by weight dispersant (manufactured by BYK Chemie "DisperBYK 16").
1 "); 2 parts by weight surfactant (" Emulgen 104P "manufactured by Kao Corporation); 2 parts by weight surfactant (" S-381 "manufactured by Asahi Glass Co., Ltd.); 0.3 parts by weight

For the negative-working photosensitive lithographic printing plate thus obtained,
Violet laser exposure machine with wavelength 410nm (Esc
scanning exposure with various exposure energies by using Her-Grad's "Cobalt 8", and then 0.7% by weight of sodium carbonate and 0.5% by weight of an anionic surfactant (Kao's "Perex NBL"). % Aqueous solution at 28 ° C. for 30 seconds and then washed with water to prepare a negative lithographic printing plate on which scanning line images were formed. The sensitivity determined from the minimum exposure energy for forming a scanning line image was 20 μJ / cm ² .

A negative lithographic printing plate exposed with the minimum exposure energy as described above and developed was used.
The printing process and the regenerating process were performed in the same manner as in. The degree of residual line image after reproduction of the aluminum support after printing is rank A, and reproduction and printing were performed in the same manner as in Example 1
After repeating 10 times, a negative type lithographic printing plate was prepared using an aluminum support which had been regenerated 10 times, and the sensitivity was 20 μJ / cm ² which was the same as before reproduction.
When printing was performed using a negative lithographic printing plate that was exposed with an exposure energy of J / cm ² and developed, a high-quality printed matter was obtained after printing 1,000 sheets.

The negative photosensitive lithographic printing plate prepared by using the recycled aluminum support was 40 W.
Of the yellow fluorescent lamp (40W yellow fluorescent lamp "Neorumi Super FLR40S-Y / M" manufactured by Mitsubishi Electric Corp.) at a light intensity of 400 lux for 30 minutes, and then the same development processing as above is performed. As a result, it was confirmed that the photosensitive layer was completely dissolved and removed, and the safelight property under a yellow lamp was good.

Example 5: Aluminum plate (thickness 0.24
mm) in a 5% by weight aqueous solution of sodium hydroxide to 60
After degreasing at 1 ° C for 1 minute, in a hydrochloric acid aqueous solution having a concentration of 0.5 mol / liter, temperature 25 ° C, current density 60A / d.
The electrolytic etching treatment was performed under the conditions of m ² and a treatment time of 30 seconds. Then, after desmutting treatment in a 5 wt% sodium hydroxide aqueous solution at 60 ° C. for 10 seconds, the temperature was 20 ° C. in a 20 wt% sulfuric acid solution at a current density of 3 A / d.
Anodizing treatment was performed under the conditions of m ² and treatment time of 1 minute. Then, hot water sealing treatment was performed with hot water at 80 ° C. for 20 seconds to obtain an aluminum support for a lithographic printing plate. The value of the average roughness Ra of the aluminum support measured by a surface roughness meter (“SE-3DH” manufactured by Kosaka Laboratory Ltd.) is 0.60 μm.
It was m.

Then, the positive type photosensitive composition was coated on the surface of the obtained aluminum support with a wire bar and dried to form a photosensitive layer, whereby a negative type photosensitive lithographic printing plate was prepared. The positive photosensitive composition as a coating liquid was prepared by stirring the following components (A), a photothermal conversion substance, and (B), an alkali-soluble resin, in 1000 parts by weight of methyl cellosolve at room temperature. The coating liquid was dried at 100 ° C. for 2 minutes, and the dried film thickness after coating was 2.4 μm.

[0260]

[Table 11] (A) Photothermal conversion substance Indole dye shown in the above-mentioned specific example (II-9);
3 parts by weight (B) Alkali-soluble resin Phenol: m-cresol: p-cresol Novolak resin (Mw 9,400) consisting of a polycondensate of mixed phenols and formaldehyde in a molar ratio of 50:30:20 100 parts by weight Crystal Violet Lactone; 3 parts by weight

Next, the obtained positive type photosensitive lithographic printing plate was exposed to an exposure apparatus (“Trend Setter” manufactured by Creo Co., Ltd.) using a semiconductor laser having a wavelength of 830 nm as a light source.
3244T ”) and various exposure energies for 20
Scanning exposure was performed on a half-tone image of 0 line and 1 to 99%. And
28 ° C alkaline developer ("DP" manufactured by Fuji Photo Film Co., Ltd.
-4 "8 times diluted solution) for 30 minutes and then washed with water to obtain a positive type lithographic printing plate in which a dot image of 1 to 99% is reproduced. The sensitivity at that time was 150 J / cm ² as the exposure energy for reproducing a halftone dot image of 3%.

Printing was carried out using the positive type lithographic printing plate which was exposed with the above-mentioned exposure energy and developed.
In the printing process, after the positive planographic printing plate was detachably fixed to the plate cylinder of a planographic printing machine (“Diamond F-2” manufactured by Mitsubishi Heavy Industries, Ltd.), the positive type planographic printing plate was wetted. Dampening water from the water supply mechanism ("Astro N" manufactured by Nikken Chemical Co., Ltd.
o. 1 mark II ”) was supplied, and printing ink (“ Hychomagenta ”manufactured by Toyo Ink Co., Ltd.) was supplied from the printing ink supply mechanism to print 10,000 sheets.

After the printing is completed, the planographic printing plate is still fixed to the plate cylinder, and after the printing ink on the plate surface is washed and removed, the image removing mechanism attached to the printing machine is fixed to the plate cylinder. The release agent for removing the image was applied to the plate surface by the roller No. 1 to dissolve the positive image. As the release agent, an aqueous solution of dimethylpolysiloxane, 5% by weight of diethanolamine, 16% by weight of phenoxyethanol, an anionic surfactant, and 6% by weight of sodium dibutylnaphthalenesulfonate was used. Then, wipe the image with gauze to remove the image, and then wash with water.
The aluminum support was regenerated.

Subsequently, the surface of the regenerated aluminum support was again coated with the same coating liquid as the positive photosensitive composition described above by the roller of the coating liquid coating mechanism attached to the printing machine. A positive photosensitive lithographic printing plate was prepared by heating and drying to form a photosensitive layer. Then, again, using the exposure mechanism, after scanning and exposing the above-mentioned photosensitive layer with a laser light source, using the roller of the development processing mechanism attached to the printing machine, in the same manner as described above for the photosensitive layer. By developing, a positive image was revealed and a positive planographic printing plate was produced. The sensitivity at that time is 3
The exposure energy required to reproduce a halftone dot image was 150 J / cm ^2, which was the same as before reproduction.

Then, using the above positive type lithographic printing plate exposed and developed with an exposure energy of 150 mJ / cm ² , a second printing was carried out in the same manner as above,
High quality prints were obtained on 1,000 prints. Further, similarly, the lithographic printing plate after the second printing was repeatedly reproduced and printed, and the plate was reproduced 10 times. The sensitivity at that time was 150 mJ, which was the same as before the reproduction.
/ M ² , and high-quality printed matter was obtained after printing 1,000 sheets using the printing plate.

Regarding the above-mentioned positive type photosensitive lithographic printing plate prepared by using the aluminum support after being regenerated 10 times, a white fluorescent lamp (36W white fluorescent lamp "Neolmi Super FLR40S-W / M manufactured by Mitsubishi Electric Corporation" was used. / 36 ") light 4
After leaving under irradiation with a light intensity of 00 lux for 10 hours, the same developing treatment as above was carried out, and it was confirmed that there was no substantial film reduction and the safelight property under a white lamp was good. .

Comparative Example 1: The same process as in Example 1 was repeated except that methyl ethyl ketone was used as the stripping solution, and printing and recycling of the printing plate were repeated 4 times. The pigment component of the printing ink was found to remain on the non-image area of the printing plate. And 4
When printing was performed in the same manner using the printing plate obtained in the second reproduction, stains due to the printing ink were found on the non-image portion of the printed matter.

[0268]

As described above, according to the method of regenerating a lithographic printing plate according to the present invention, the image portion of the planographic printing plate after printing is removed and the image portion is regenerated when the aluminum support is regenerated. By using an alkaline water solution with a specific pH value as a release agent for removal, the image area can be easily and reliably removed, and the printing ink remaining on the image area can be removed by lithographic printing. Prevents redeposition on the non-image area of the plate and keeps the hydrophilicity of the non-image area, so it is possible to further reduce stains caused by printing ink when the photosensitive lithographic printing plate is regenerated, and as a result, regenerated lithographic printing Even in printing with a plate, a high-quality printed matter can be obtained without stains due to ink adhesion on the non-image area.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ identification code FI theme code (reference) G03F 7/038 501 G03F 7/038 501 (72) Inventor Takuya Uematsu 1000 Kamoshida-cho, Aoba-ku, Yokohama-shi, Kanagawa Mitsubishi Chemical Co., Ltd. (72) Inventor Mizuho Uji 1000 Kamoshida-cho, Aoba-ku, Yokohama, Kanagawa Prefecture F-term (reference) 2H025 AB03 AC08 AD01 AD03 BC32 BC42 CA18 CA27 CA28 CA39 CA41 CA50 CB13 CB14 CB43 DA18 FA03 FA14 FA47 2H096 AA07 BA20 CA20 EA04 GA01 JA04 LA02

Claims (9)

[Claims] 1. A photosensitive lithographic printing plate comprising a photosensitive layer formed on the surface of an aluminum support and fixed on a plate cylinder of a printing machine, and the photosensitive layer is scanned and exposed by a laser light source, After developing and exposing the image to form a lithographic printing plate, printing ink is supplied to print on the printing material, and then the image is removed with a release agent to regenerate the aluminum support, and then again. In the method for reproducing a lithographic printing plate, which comprises forming a photosensitive layer on the surface of an aluminum support and reproducing the photosensitive lithographic printing plate, a pH of 1 is used as the release agent.
A method of regenerating a lithographic printing plate, which comprises using an alkaline aqueous solution of 0 or more. 2. The method for producing a lithographic printing plate according to claim 1, wherein the release agent contains a water-soluble organic solvent. 3. The method of regenerating a lithographic printing plate according to claim 1, wherein the release agent contains at least one of a neutral, anionic or amphoteric surfactant. 4. The laser light source is 400 to 420n
The method for regenerating a lithographic printing plate according to claim 1, wherein a laser light source that emits laser light in the wavelength range of m or a laser light source that emits laser light in the wavelength range of 600 to 1300 nm is used. 5. The photosensitive composition comprises an ethylenically unsaturated compound, 350 to 420 nm in the blue-ultraviolet region or 600 to 420 nm.
5. A photopolymerizable composition containing a light absorbing dye having a maximum absorption in the near infrared region of 1300 nm as a photopolymerizing agent, a photopolymerization initiator, and a polymer binder. Reproduction method of lithographic printing plate described in. 6. The method of reproducing a lithographic printing plate according to claim 5, wherein the light absorbing dye is a dye having a structure in which heteroatoms are bonded via a polymethine chain. 7. The photosensitive composition comprises 600 to 1300 nm.
5. A positive type photosensitive composition comprising a photothermal conversion substance having an absorption maximum at 1, and absorbing light from an image exposure light source to convert it into heat, and an alkali-soluble resin. How to regenerate lithographic printing plates. 8. The method for regenerating a lithographic printing plate according to claim 7, wherein the photothermal conversion substance is a dye having a structure in which heteroatoms are bonded via a polymethine chain. 9. The method for recycling a lithographic printing plate according to claim 7, wherein the alkali-soluble resin is a novolac resin.