JP2008003584A - Lithographic printing plate precursor and stack thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a lithographic printing plate precursor capable of suppressing scratching between a surface of a photosensitive layer or a protective layer and a back surface of an aluminum support even when such lithographic printing plate precursors are stacked without interposing a slip sheet, and to provide a stack of such lithographic printing plate precursors. <P>SOLUTION: The lithographic printing plate precursor has a photosensitive layer that has sensitivity to laser light and is provided on or above a surface of a support, wherein an average surface roughness (Ra) of a back surface of the support in both of a longitudinal direction and a width direction is ≤0.15 μm. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a lithographic printing plate precursor and a laminate thereof. More specifically, the present invention relates to a lithographic printing plate precursor suitable for a negative lithographic printing plate precursor, capable of direct drawing with a laser beam and high-speed processing. In particular, the present invention relates to a planographic printing plate precursor having improved scratch resistance between recording materials even when a plurality of planographic printing plate precursors are laminated, and a laminate of a planographic printing plate precursor using the same.

  Conventionally, as a lithographic printing plate precursor, a PS plate having a configuration in which an oleophilic photosensitive resin layer is provided on a hydrophilic support is widely used. As the plate making method, mask exposure is usually performed through a lithographic film. After (surface exposure), the desired printing plate was obtained by dissolving and removing the non-image area. In recent years, digitization techniques that electronically process, store, and output image information using a computer have become widespread. Various new image output methods corresponding to such digitization techniques have come into practical use. As a result, computer-to-plate (CTP) technology that scans highly directional light such as laser light according to digitized image information and directly produces a printing plate without going through a lithographic film is eagerly desired. Obtaining a lithographic printing plate precursor adapted to this is an important technical issue.

As such a lithographic printing plate precursor capable of scanning exposure, an oleophilic photosensitive resin layer containing a photosensitive compound capable of generating active species such as radicals and Bronsted acid by laser exposure on a hydrophilic support (hereinafter referred to as “lithographic printing plate precursor”) , Which is also referred to as a photosensitive layer) has been proposed and is already on the market. This lithographic printing plate precursor is laser-scanned based on digital information to generate active species, which causes physical or chemical changes in the photosensitive layer to insolubilize it, followed by development processing, thereby developing a negative lithographic printing plate Can be obtained.
In particular, a photopolymerization type photosensitive layer containing a photopolymerization initiator having excellent photosensitive speed, an addition-polymerizable ethylenically unsaturated compound, and a binder polymer soluble in an alkali developer, on a hydrophilic support, and A lithographic printing plate precursor (see, for example, Patent Document 1) provided with an oxygen-blocking protective layer as necessary is advantageous in that it is excellent in productivity, is easy to develop, and has good resolution and thickness. Have desirable printing performance.

In addition, in order to further improve productivity, that is, in order to improve plate-making speed, photopolymerizability comprising a cyanine dye having a specific structure, an iodonium salt and an addition-polymerizable compound having an ethylenically unsaturated double bond. There has been proposed a recording material that uses the composition for a photosensitive layer and does not require heat treatment after imagewise exposure (see, for example, Patent Document 2). However, this recording material has a problem that the polymerization is inhibited by oxygen in the air during the polymerization reaction, resulting in a decrease in sensitivity and insufficient strength of the formed image area.
To solve this problem, a method of providing a protective layer containing a water-soluble polymer on the photosensitive layer or a method of providing a protective layer containing an inorganic layered compound and a water-soluble polymer (for example, see Patent Document 3) is known. It has been. The presence of these protective layers prevents polymerization inhibition, promotes the curing reaction of the photosensitive layer, and improves the strength of the image area.

By the way, it is important to shorten the time required for the exposure process as productivity in the plate making operation of a photopolymerization type lithographic printing plate precursor that is easy to develop.
In the exposure process, the lithographic printing plate precursor usually has a function of preventing adhesion between the original plates, and a function of preventing scratches caused by rubbing the surface of the relatively soft protective layer with the aluminum support between the original plates. ”Is supplied as a laminated body, but the interleaf removal time in the exposure process is a cause of inefficiency in plate making operations. In order to increase the efficiency in this exposure step, the step of removing the slip sheet may be omitted by using a laminate in which the slip sheet is not inserted between the original plates. However, when a laminated body into which no interleaving paper is inserted is used, there is a problem that the surface of the protective layer provided on the photosensitive layer is rubbed against the back surface of the aluminum support, so that improvement has been desired.

As described above, there is a need for a lithographic printing plate precursor that does not require interleaving when laminating a plurality of sheets, and that does not cause scratches on the printing plate surface during manufacturing, storage, and plate making operations. However, it has not been provided yet.
Japanese Patent Laid-Open No. 10-228109 Japanese Examined Patent Publication No. 7-103171 JP 11-38633 A

An object of the present invention is to solve the conventional problems and achieve the following objects.
That is, an object of the present invention is to provide a planographic printing that can reduce scratches generated between the surface of the photosensitive layer or the protective layer and the back surface of the aluminum support even when the planographic printing plate precursor is laminated without interposing the interleaf. It is to provide a laminate of a plate precursor and a planographic printing plate precursor.

As a result of intensive studies to achieve the above object, the present inventor has found that the above object can be achieved by controlling the surface roughness of the back surface of the support, and has completed the present invention.
That is, the present invention is as follows.
(1) A lithographic printing plate precursor provided with a photosensitive layer sensitive to laser light on the surface of a support, wherein the average surface roughness (Ra) in the longitudinal and width directions of the back surface of the support is All of the planographic printing plate precursors are 0.15 μm or less.
(2) The lithographic printing plate precursor as described in (1), wherein the average surface roughness (Ra) in the longitudinal direction and the width direction of the back surface of the support is 0.13 μm or less.
(3) The lithographic printing plate precursor as described in (1) or (2), wherein the support comprises aluminum.
(4) The lithographic printing according to any one of (1) to (3), wherein the Bekk smoothness of the surface sensitive to laser light of the lithographic printing plate precursor is 10,000 seconds or less Version original edition.
(5) The lithographic printing plate precursor as described in any one of (1) to (4), wherein the photosensitive layer contains a photosensitive polymerization initiator.
(6) The lithographic printing plate precursor as described in any one of (1) to (5), which has a protective layer on the photosensitive layer.
(7) The lithographic printing plate precursor as described in (6), wherein the protective layer has a filler.
(8) The lithographic printing plate precursor as described in any one of (1) to (7), wherein the photosensitive layer contains an infrared absorbing dye having a maximum absorption wavelength between 750 nm and 1400 nm.
(9) The lithographic printing plate precursor as described in any one of (1) to (7), wherein the photosensitive layer contains a sensitizing dye having a maximum absorption wavelength between 350 nm and 450 nm.
(10) A lithographic printing plate comprising a plurality of laminated layers in direct contact with the uppermost layer of the lithographic printing plate precursor as described in any one of (1) to (9) and the back surface of the support The original laminate.

  According to the present invention, a lithographic printing plate precursor capable of reducing scratches generated between the surface of the photosensitive layer or the protective layer and the back surface of the aluminum support even when the lithographic printing plate precursor is laminated without sandwiching the interleaving paper. And a laminate of a lithographic printing plate precursor.

<Lithographic printing plate precursor>
The lithographic printing plate precursor according to the present invention is a lithographic printing plate precursor in which a support and a photosensitive layer sensitive to laser light are provided on the surface of the support, the longitudinal direction and the width of the back surface of the support. The average surface roughness (Ra) in the direction is 0.15 μm or less.
Hereinafter, the support, the back surface of the support and the photosensitive layer will be specifically described.

[Support]
As the support for the lithographic printing plate precursor in the invention, a conventionally known hydrophilic support for use in the lithographic printing plate precursor can be used without limitation.
The support used is preferably a dimensionally stable plate, for example, paper, paper laminated with plastic (eg, polyethylene, polypropylene, polystyrene, etc.), metal plate (eg, aluminum, zinc). , Copper, etc.), plastic films (eg, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polyester, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.), Paper or plastic film, etc., laminated or vapor-deposited with metals as described above are included. For these purposes, if necessary, for the purpose of imparting hydrophilicity or improving strength, appropriate known physical and chemical Processing It may be.

  Among these, paper, a polyester film or an aluminum plate can be cited as a preferred support, which has good dimensional stability, is relatively inexpensive, and can provide a surface with excellent hydrophilicity and strength by surface treatment as required. An aluminum plate is more preferable. A composite sheet in which an aluminum sheet is bonded on a polyethylene terephthalate film as described in Japanese Patent Publication No. 48-18327 is also preferable.

An aluminum plate is a metal plate mainly composed of dimensionally stable aluminum. In addition to a pure aluminum plate, an alloy plate containing aluminum as a main component and containing a trace amount of foreign elements, or aluminum (alloy) is laminated. Or it is chosen from the vapor-deposited plastic film or paper. In the following description, the above-mentioned support made of aluminum or an aluminum alloy is generically used as an aluminum support. The foreign elements contained in the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, titanium, and the content of foreign elements in the alloy is 10% by mass or less. Is preferred. In the present invention, a pure aluminum plate is suitable, but since completely pure aluminum is difficult to manufacture in the refining technique, it may contain a slightly different element. Thus, the composition of the aluminum plate applied to the present invention is not specified, and it is a conventionally known material such as JIS A 1050, JIS A 1100, JIS A 3103, JIS A 3005, etc. Can be used as appropriate.
Moreover, the thickness of the aluminum support body used for this invention is about 0.1 mm-0.6 mm. This thickness can be appropriately changed depending on the size of the printing press, the size of the printing plate, and the user's desire. The aluminum support may be subjected to a support surface treatment described later as necessary. Of course, it may not be applied.

[Back side of support]
In the planographic printing plate precursor of the present invention, the average surface roughness Ra in the longitudinal direction and the width direction of the back surface of the support is both from the viewpoint of reducing scratches generated between the protective layer surface and the back surface of the aluminum support. It needs to be 0.15 μm or less. Preferably, Ra needs to be 0.13 μm or less. Here, the average surface roughness (arithmetic average roughness) (Ra) is a portion of the measurement length L in the direction of the center line from the roughness curve measured with a stylus meter, and the center line of the extracted portion Is the X axis, the axis orthogonal thereto is the Y axis, and the roughness curve is represented by Y = f (X), the value given by the following equation is expressed in μm units (determining L and The average roughness is measured according to JIS B 0601).

FIG. 1 shows a perspective view of a first embodiment of a planographic printing plate precursor according to the present invention. The planographic printing plate precursor 10 has a structure in which a support 12 and a direct-drawing type photosensitive layer 14 are provided on a surface 12 a of the support 12. The back surface 12b of the support 12 may have the same average surface roughness Ra in the longitudinal direction (arrow x in the drawing) and the width direction (arrow y in the drawing), or have different average surface roughness (Ra). May be. Hereinafter, in this specification, the average surface roughness in the width direction is referred to as Ral, and the average surface roughness in the longitudinal direction is referred to as Ras.
FIG. 2 is a perspective view of the lithographic printing plate precursor in a state of being wound into a roll at the time of cutting in order to further describe the longitudinal direction and the width direction of the lithographic printing plate precursor. The lithographic printing plate precursor 10 is produced, for example, in the form of a web through the steps described below, and is usually temporarily stored in a rolled state 10 ′ as shown in FIG. And cut into a desired length. In the planographic printing plate precursor 10, the back surface 12 b of the support 12 may have an average surface roughness (Ra) that is different in the longitudinal direction and the width direction, or may be the same. Such a planographic printing plate precursor 10 is stored in a stacked state 10 ″, as will be described later, until it is subjected to a plate making process or the like.
FIG. 3 is a flowchart showing an example of a general manufacturing process for manufacturing the lithographic printing plate precursor 10. The manufacturing process shown in FIG. 3 is an example in which an aluminum alloy plate is used as a support. For convenience of explanation, the process is simplified.

(Method for producing planographic printing plate precursor)
-Cleaning treatment of molten aluminum-
First, the molten aluminum alloy is cleaned to remove unnecessary gases such as hydrogen and solid impurities mixed in the molten metal. Examples of the cleaning treatment include flux treatment, degassing treatment using argon gas, chlorine gas, and the like as treatment for removing unnecessary gas. Examples of the treatment for removing impurities include so-called rigid media filters such as ceramic tube filters and ceramic foam filters, filters using alumina flakes and alumina balls as a filter medium, and filtering treatment using a glass cloth filter. . Moreover, the cleaning process which combined the degassing process and the filtering process can also be performed.

-Casting of molten aluminum-
Next, a molten aluminum is cast. As a casting method, there are a method using a fixed mold represented by a DC casting method and a method using a driving mold represented by a continuous casting method. For example, when DC casting is performed, an ingot having a predetermined plate thickness (for example, 300 to 800 mm) is manufactured using a fixed mold. The obtained ingot is chamfered according to a conventional method, and 1 to 30 mm, preferably 1 to 10 mm, of the surface layer is cut to obtain a plate-like body of an aluminum alloy having a desired plate thickness. On the other hand, in the continuous casting method, an aluminum alloy plate-like body having a predetermined thickness can be continuously obtained by inserting a molten aluminum alloy between a pair of twin belts. The obtained plate-like body may be subjected to a soaking treatment as necessary. When performing the soaking treatment, it is preferable to perform the heat treatment at 450 to 620 ° C. for 1 hour or more and 48 hours or less so that the intermetallic compound does not become coarse. When it is shorter than 1 hour, the effect of the soaking treatment is insufficient.

-Hot rolling treatment, cold rolling treatment, and adjustment of the surface roughness of the back surface of the support-
Next, the plate-like body is subjected to hot rolling and cold rolling to obtain an aluminum alloy rolled plate. The plate-like body can be rolled by inserting the plate-like body between a pair of rolls. The hot rolling start temperature is preferably 350 to 500 ° C. An intermediate annealing treatment can also be performed before cold rolling, after cold rolling, or during cold rolling. The intermediate annealing treatment can be performed using a batch-type annealing furnace. In that case, the intermediate annealing treatment is usually performed at 280 ° C. to 600 ° C. for 2 to 20 hours, preferably 350 to 500 ° C. for 2 to 10 hours. The intermediate annealing treatment may be performed using a continuous annealing furnace. In that case, heating is usually performed at 400 to 600 ° C. for 360 seconds or less, preferably 450 to 550 ° C. for 120 seconds or less. It is preferable to use a continuous annealing furnace and raise the temperature at 10 ° C./second or more because the crystal structure in the resulting molded body can be made finer. After hot rolling, if necessary, intermediate annealing treatment is performed, cold rolling is performed, and finally an aluminum alloy plate having a thickness of 0.1 to 0.5 mm is obtained. It is preferable that the obtained aluminum alloy plate is further processed by a correction device such as a roller leveler or a tension leveler because the flatness of the aluminum plate is improved. Moreover, when it is necessary to make a board width into a predetermined width, it can adjust to a predetermined width through a slitter line.

  In the cold rolling step, by transferring the pattern of the rolling roll onto the back surface of the aluminum alloy plate, the back surface of the aluminum alloy plate can have the average surface roughness, that is, Ra of 0.15 μm or less. Moreover, in the said correction process, you may transfer this pattern to the back surface of a support body using the roll which has a pattern of predetermined surface roughness. In the above method, it is preferable that the back surface has a predetermined average surface roughness because it is not necessary to separately provide a step of adjusting the surface roughness of the back surface of the support, and the process can be simplified. For example, the back surface of the support is subjected to cold rolling using a roll having a pattern in which the average surface roughness in the rotation direction of the roll is different from the average surface roughness in the direction perpendicular to the rotation direction of the roll. Thus, the average surface roughness can be made different in the longitudinal direction and the width direction.

-Roughening treatment of support surface-
In the cold rolling process or the straightening process, the aluminum alloy plate whose back surface is adjusted to a predetermined average surface roughness is then subjected to a roughening process on the surface (the surface on which the photosensitive layer is provided). Examples of the roughening treatment include mechanical roughening treatment, chemical roughening treatment, and electrochemical roughening treatment. These may be implemented alone or in combination. For example, an electrochemical roughening treatment may be performed after a mechanical roughening treatment using a brush or the like. Examples of the mechanical surface roughening treatment include ball grain, wire grain, brushing rain, and liquid honing. In addition, for example, a mechanical surface roughening method described in JP-A-6-135175 and JP-B-50-40047 can be employed. When the mechanical surface roughening treatment is performed, the surface of the aluminum alloy plate can usually be set to an average surface roughness (Ra) of 0.35 to 1.0 μm. Examples of the chemical roughening treatment include a method of immersing an aluminum alloy plate in an alkaline bath.

  The electrochemical roughening treatment is easy to give fine irregularities to the surface of the aluminum alloy plate, and as a result, the adhesion between the photosensitive layer 14 and the support 12 can be improved. It is valid. The electrochemical surface roughening treatment is usually performed by passing a direct current or an alternating current through an aluminum alloy plate using an acid such as nitric acid or hydrochloric acid as an electrolyte. When the electrochemical surface roughening treatment is performed, craters or honeycomb-like pits having an average diameter of about 0.5 to 20 μm are usually formed at an area ratio of 30 to 100% with respect to the surface of the aluminum alloy plate. be able to. The formed pits have the effect of reducing the stain on the non-image area of the planographic printing plate and the effect of improving the printing durability. In the electrochemical treatment, by adjusting the quantity of electricity during electrolysis, that is, the product of the current during electrolysis and the time during which the current is passed, the shape of the pits formed, the area ratio of the pits, etc. are adjusted. Can do.

  Before and after the roughening treatment, the surface of the aluminum alloy plate may be etched with an alkali agent such as caustic soda or caustic potash. Furthermore, when the etching process is performed, a desmut process with an acid may be performed after the etching process to remove an alkali-insoluble substance (smut) remaining on the surface of the aluminum plate. In particular, when performing an electrochemical surface roughening treatment, it is preferable to perform the etching treatment and the desmut treatment before and after the surface roughening treatment.

-Anodizing treatment-
After the surface of the aluminum alloy plate is roughened, it is preferable to further perform anodization. Anodizing is preferable because an anodic oxide film is formed on the surface of the aluminum alloy plate and wear resistance is improved. The anodized film can be formed by immersing an aluminum alloy plate as an electrode in an electrolytic solution and passing an electric current therethrough. As currents to be communicated, currents of various waveforms such as direct current and alternating current are selected according to the purpose. Any electrolytic solution may be used as long as it forms a porous oxide film on the surface of the aluminum alloy plate. In general, sulfuric acid, phosphoric acid, oxalic acid, chromic acid, or a mixture thereof is used. The concentration of the electrolyte in the electrolytic solution is appropriately determined depending on the type of the electrolyte. Various conditions such as the concentration of the electrolyte in the electrolytic solution and the electrolysis time cannot be defined unconditionally because the preferred range varies depending on the electrolyte used, etc., but in general, the concentration of the electrolyte is 1 to 80 weights. %, Liquid temperature of 5 to 70 ° C., current density of 1 to 60 A / dm ² , voltage of 1 to 100 V, and electrolysis time of 10 seconds to 300 seconds are appropriate. The amount of the anodized film formed by the anodizing treatment is usually preferably ¹ to 6 g / m ² .

When the surface of the aluminum alloy plate (the surface on which the photosensitive layer is provided) is anodized, it is preferable that the back surface is also anodized. When an anodized film is formed on the back side, the back side is less likely to be scratched, so that when the lithographic printing plate precursor is stacked and wound on a roll, the back side scratches are transferred to the photosensitive layer. Can be prevented. Moreover, since the hardness of the back surface of a support body will improve if an anodized film is formed, even when the frictional force between a conveyance belt and a conveyance roll is added to the back surface, it can prevent generating attrition powder. The anodizing treatment on the front and back surfaces of the aluminum alloy plate can be performed using, for example, the apparatus shown in FIG.
An anodizing apparatus 20 shown in FIG. 4 includes a power supply tank 22 and an electrolytic treatment tank 24. The power supply tank 22 is filled with an electrolyte solution 26 and is disposed to face the surface on the photosensitive layer forming side of the aluminum alloy plate 30 to which the power supply electrode 28 is conveyed. On the other hand, the electrolytic treatment tank 24 is filled with an electrolytic solution 32, and an electrolytic electrode 34 is disposed facing the photosensitive layer forming surface side and the back surface side of the aluminum alloy plate being conveyed. The aluminum alloy plate 30 passes through the power supply tank 22 and the electrolytic treatment tank 24 by the conveying roller 36, and an anodized film is formed on the surface and the back surface of the aluminum alloy plate 30 on the photosensitive layer forming side.

The amount of the anodized film formed on the back surface of the aluminum alloy plate is preferably 0.1 g / m ² or more, and more preferably 0.5 g / m ² or more. When the coating amount is less than 0.1 g / m ² , the effect of improving the strength of the back surface may not be sufficiently obtained. On the other hand, the upper limit of the coating amount is not particularly limited, but it is preferably 4 g / m ² or less from the viewpoint of both strength improvement effect and production cost.

  After the anodizing treatment, a sealing treatment may be performed as desired. The sealing treatment is performed by a method of immersing the anodized support in hot water or a hot aqueous solution containing an inorganic salt or an organic salt, a method of exposing to a steam bath, or the like.

  Further, after the anodizing treatment, an interface control treatment such as a hydrophilic treatment may be performed as desired. Examples of the interface control treatment include alkali metal silicate (for example, sodium silicate aqueous solution) methods as disclosed in US Pat. Nos. 2,714,066, 3,181,461, 3,280,734 and 3,902,734. In this method, the support is immersed in an aqueous sodium silicate solution or electrolytically treated. In addition, treatment with potassium fluorinated zirconate disclosed in Japanese Patent Publication No. 36-22063 and polyvinylphosphonic acid as disclosed in US Pat. Nos. 3,276,868, 4,153,461 and 4,689,272 The method etc. are mentioned.

-Application, drying and cutting of photosensitive layer coating solution-
Next, the photosensitive layer 14 is formed on the support 12 having the back surface 12b roughened to a predetermined average surface roughness and the surface 12a roughened and anodized. The photosensitive layer 14 can be formed by applying a coating solution prepared by dissolving or dispersing each component constituting the photosensitive layer in a solvent onto the surface 12a of the support 12 and drying. As the coating method, for example, bar coater coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating, roll coating method, and the like can be used. A photosensitive layer having a multilayer structure can be formed by repeating the coating appropriately. Further, a plurality of photosensitive layers can be simultaneously applied and formed.
After the photosensitive layer 14 is formed, as shown in FIG. 2, it is wound into a roll and then cut into a desired size.

(Photosensitive layer)
In the lithographic printing plate precursor according to the invention, a photosensitive layer sensitive to laser light is provided on a support. The photosensitive layer comprises (A) a binder polymer, (B) a compound having an addition-polymerizable ethylenically unsaturated bond, (C) a light or thermal polymerization initiator, (D) a sensitizing dye, and (E) other components. It is preferable to contain. Details will be described below.

((A) binder polymer)
As the (A) binder polymer (hereinafter appropriately referred to as “component (A)”) used for the photosensitive layer in the present invention, any conventionally known one can be used without limitation, but a binder polymer having film-forming properties is preferred. Examples of such binder polymers include acrylic resins, polyvinyl acetal resins, polyurethane resins, polyurea resins, polyimide resins, polyamide resins, epoxy resins, methacrylic resins, polystyrene resins, novolac phenolic resins, polyester resins, and synthetic rubbers. And natural rubber.
The binder polymer may have crosslinkability in order to improve the film strength of the image area. In order to impart crosslinkability to the binder polymer, a crosslinkable functional group such as an ethylenically unsaturated bond may be introduced into the main chain or side chain of the polymer. The crosslinkable functional group may be introduced by copolymerizing a monomer having such a functional group.

  From the viewpoint of alkali solubility, the binder polymer has a structure having an acid group having an acid dissociation constant (pKa) of 0 or more and 11 or less in the polymer side chain, for example, a structure represented by the following general formula (1). It is preferable to have it.

In the general formula (1), P represents a polymer main chain skeleton, and X represents a single bond or a carboxylic acid ester group (—COO—), an amide group (—CONH—), or a hydrocarbon directly bonded to the polymer main chain skeleton. And a linking group selected from the group consisting of a group and an ether group (—O— or —S—).
AH represents a partial structure that functions as an acid group having an acid dissociation constant (pKa) of 0 or more and 11 or less. m represents an integer of 1 to 5.
The acid groups that can be contained in the alkali-soluble binder and have an acid dissociation constant (pKa) of 0 or more and less than 5.5 and 5.5 or more and 11 or less will be described below.

1. Acid groups having an acid dissociation constant (pKa) of 0 or more and less than 5.5 Examples of acid groups having an acid dissociation constant (pKa) of 0 or more and less than 5.5 include sulfonic acid groups, phosphoric acid groups, and carboxylic acid groups. Particularly preferred are carboxylic acid groups. Specific examples of the structure containing a carboxylic acid group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, incrotonic acid, maleic acid, and p-carboxylstyrene. These are acid, methacrylic acid, and p-carboxylstyrene, and one or more of these can be used.

2. Acid group having acid dissociation constant (pKa) of 5.5 to 11 In the present invention, the acid dissociation constant (pKa) of 5.5 to 11 of the acid groups contained in the alkali-soluble polymer will be described. pKa is preferably in the range of 7-11, more preferably in the range of 8-11.
Specifically, as such an acid group, for example, a phenol group (pKa = 9.99), a 2-methoxyphenol group (pKa = 9.99), a 2-chlorophenol group (pKa = 8.55), 2-hydroxybenzoic acid methyl group (pKa = 9.87), 4-methylphenol group (pKa = 10.28), 1,3-benzenediol group (pKa = 9.20), 1-naphthol group (pKa = 9.30), 1,2-benzenediol group (pKa = 9.45), benzenesulfonamide group (pKa = 10.00), N-acetylphenylbenzenesulfonamide group (pKa = 6.94), 4- Aminobenzenesulfonamide group (pKa = 10.58), N-phenyl-4-aminobenzenesulfonamide group (pKa = 6.30), N- (4-acetylphenyl) 4-amino-benzenesulfonamide group (pKa = 7.61), and the like acetyl ethyl acetate group (pKa = 10.68) is. Among these, a phenol group that may have a substituent on the aromatic group and a benzenesulfonamide group that may have a substituent on the aromatic group are more preferable.

  The acid dissociation constant pKa described in the above specific examples is E.I. P. SERJEANT et al., “IONISATION CONSTRANTS OF ORGANIC ACIDS IN AQUEOUS SOLUTION” and JOHN A. It is a numerical value described in DEAN, “LANGE'S HANDBOOK OF CHEMISTRY”.

  The structural unit having the specific acid group is preferably a structural unit represented by the following general formula (2).

In the general formula (2), X ¹ represents O, S, or —NR ⁴ —.
Y represents a divalent organic group.
A ¹ represents a specific acid group.
R ¹ , R ² , R ³ , and R ⁴ each independently represent a hydrogen atom, a halogen atom, a monovalent organic group, a cyano group, or a nitro group.

In the general formula (2), examples of the monovalent organic group represented by R ¹ , R ² , R ³ , and R ⁴ include a linear, branched, or cyclic alkyl group, an aromatic group, and an alkoxy group. Group, acyl group, aralkyl group, alkoxycarbonyl group, aryloxy group, and the like.
The monovalent organic group may further have a substituent, and examples of the substituent that can be introduced include an alkyl group, an aryl group, an alkoxy group, an acyloxy group, a halogen atom, a hydroxy group, an amino group, A cyano group, a nitro group, etc. are mentioned.

In the general formula (2), examples of the divalent organic group represented by Y include an alkylene group, a phenylene group, and a naphthylene group.
The divalent organic group may further have a substituent. Examples of the substituent that can be introduced include an alkyl group, an aryl group, an alkoxy group, an acyloxy group, a halogen atom, a hydroxy group, an amino group, A cyano group, a nitro group, etc. are mentioned.

  Moreover, as a structural unit having a specific acid group that can be used in the present invention, a structural unit derived from a monomer represented by the following general formula (3), (6), or (7), or the following general formula (4) The structural units represented by (5) and (8) are also preferred.

In general formula (3), R ⁵ represents a hydrogen atom or an alkyl group.
X ² represents a divalent linking group.
Y ¹ represents a divalent aromatic group which may have a substituent.
In the general formula (3), examples of the divalent linking group represented by X ² include an alkylene group which may have a substituent or a phenylene group.
Examples of the divalent aromatic group that may have a substituent represented by Y ¹ include a phenylene group or a naphthylene group that may have a substituent.

In General Formula (4), R ⁶ and R ⁷ each independently represent a hydrogen atom, an alkyl group, or a carboxylic acid group.
R ⁸ represents a hydrogen atom, a halogen atom or an alkyl group.
R ⁹ represents a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group.
X ³ represents a divalent organic group that connects a nitrogen atom and an aromatic ring carbon atom.
n represents 0 or 1.
Y ² represents a phenylene group which may have a substituent or a naphthylene group which may have a substituent.

In the structural unit represented by the general formula (4), Y ² represents a phenylene group which may have a substituent or a naphthylene group which may have a substituent. Since the characteristics of the polymerizable composition are not greatly affected, any group can be used as the substituent. Representative examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an acyl group, a hydroxy group, a carboxylic acid group, a sulfonic acid group, a cyano group, and a nitro group.

In General Formula (5), R ¹⁰ represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl group.
R ^{11 to} R ¹⁵ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an aryl group.
X ⁴ represents the atoms necessary to complete a monocyclic or polycyclic, carbocyclic aromatic ring system.
n represents 1, 2 or 3.

More preferably, as the structural unit represented by the general formula (5), R ¹⁰ is a hydrogen atom, a halogen atom, a cyano group, or an alkyl group having 1 to 6 carbon atoms, and R ¹¹ and R ¹² are each independently , A hydrogen atom, or an alkyl group having 1 to 4 carbon atoms, and R ¹³ , R ^14, and R ¹⁵ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group, or a halogen atom, This is a case where X ³ is a carbon atom necessary for completing a benzene ring or a naphthalene ring, and n is 1.

Particularly preferably, as the structural unit represented by the general formula (5), R ¹⁰ is a hydrogen atom or a methyl group, R ¹¹ , R ¹² and R ¹³ are hydrogen atoms, R ¹⁴ is a hydrogen atom and has 1 carbon atom. -4 alkyl group or halogen atom, R ¹⁵ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group or a halogen atom, and X ⁴ is a carbon necessary for completing a benzene ring or naphthalene ring. This is a case where n is 1.

When R ¹⁰ in the general formula (5) is an alkyl group, preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 or 2 carbon atoms. Particularly preferred is the case where R ¹⁰ is a hydrogen atom or a methyl group.
In the general formula (5), it is preferable that at least one of R ¹¹ and R ¹² is a hydrogen atom. If R ¹¹ and ^{R 12} represents an alkyl group, preferably a number 6 alkyl group having a carbon, and particularly preferably an alkyl group having 1 to 3 carbon atoms.

In the general formula (5), R ¹³ is preferably a hydrogen atom. R ¹⁴ is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group. R ¹⁵ is preferably an alkyl group having 1 to 4 carbon atoms or an aryl group.
In general, alkyl groups here are branched and branched, with cyclic and open chains, which may be substituted with halogen atoms or hydroxy groups, or may include ether groups or ketone groups. Not to represent saturated and unsaturated groups. An unbranched alkyl group having 1 to 4 carbon atoms is preferred. An aryl group may be monocyclic or polycyclic and represents a heterocyclic or carbocyclic aromatic ring system optionally substituted with an aryl group, alkoxy group, hydroxy group, or halogen atom.

There is no particular limitation on the position of the substituents on the ring system X ^4, governed only by preparing ease of compounds.
Carbocyclic aromatic ring system X ⁴ may be either monocyclic or polycyclic. Among the carbocyclic ring systems, mention may be made in particular of benzene and naphthalene systems.

  As a halogen atom in General formula (5), a chlorine, a bromine, and an iodine atom are preferable, and chlorine is especially preferable.

In General Formula (6) and General Formula (7), X ⁵ and X ⁶ each independently represent —O— or —NR ¹⁶ —. R ¹⁶ represents a hydrogen atom or an optionally substituted alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group.
R ¹⁷ and R ¹⁸ each independently represent —H or —CH ₃ . R ¹⁹ and R ²⁰ each independently represent an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, an arylene group, or an aralkylene group that may have a substituent.
R ²¹ represents a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group.
R ²² represents an optionally substituted alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group.

In General Formula (8), A ² represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.
B ¹ represents a phenylene group or a substituted phenylene group.
B ² represents a phenylene group optionally having a alkylene group, or a substituent having 2 to 6 carbon atoms which may have a substituent.
B ³ represents a divalent organic group.
X ⁷ and X ⁸ each independently represent —CO— or —SO ₂ —.
Y ³ represents —CO—R ²³ or —SO ₂ —R ²³ , and R ²³ represents an alkyl group, a substituted alkyl group, an aromatic group, or a substituted aromatic group.
m and j represent 0 or 1.

  Specific examples of the monomers represented by the general formulas (3), (6), and (7) and the monomers used as the structural units represented by the general formulas (4), (5), and (8) are shown below. (B-1 to B-6, C-1 to C-15, D-1 to D-6, E-1 to E-15, F-1 to F-13, G-1 to G-3, H -1 to H-2, I-1, J-1 to J-2), but is not limited thereto. These copolymerizable monomers are disclosed in JP-A-7-333839, JP-A-8-339080, JP-B-52-28401, JP-A-4-212196, JP-A-2-866, and JP-A-8-286369. It can synthesize | combine by the method as described in each gazette.

  More preferably, the binder polymer includes a polymer having a carboxylic acid as an acid group, and more preferably a polymer including a structural unit having an acid group as represented by the following general formula (9). Even after the binder polymer having a structural unit containing a carboxylic acid group in the side chain represented by the following general formula (9) is dissolved in an alkaline aqueous solution having a pH of 10 or more and left at room temperature (25 ° C.) for 60 days, It is characterized by no precipitation.

In General Formula (9), R ²⁴ represents a hydrogen atom or a methyl group, and R ²⁵ represents an (n + 1) -valent organic linking group containing an ester group represented by —O (C═O) —.
A ³ represents an oxygen atom or —NR ²⁶ —, wherein R ²⁶ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. n represents an integer of 1 to 5.

  There is no particular limitation on the means capable of suppressing the precipitation over time of the alkali-soluble polymer represented by the general formula (9) in the alkaline aqueous solution, and the polymer is due to the disappearance of the carboxyl group which is an alkali-soluble group over time. It is only necessary to be able to effectively suppress a decrease in solubility of the polymer. For example, it is highly alkali-soluble so that it can be modified in an aqueous alkali solution to introduce another functional group that exhibits alkali solubility, and improve the solubility of the entire polymer. Means such as introduction of another functional group or introduction of a structure that does not function as an alkali-soluble group but can improve solubility, for example, a structure having high affinity with an aqueous alkali solution, etc. Can take.

  Preferable specific embodiments include, for example, (I) an embodiment having a functional group that can be converted to an acid group by alkali hydrolysis in the polymer side chain represented by the following general formula (10); The aspect etc. which have an acid group whose acid dissociation constant (pKa) represented by General formula (1) is 0-11 are mentioned. Among these, since the aspect of (II) was already demonstrated, below, preferable aspects other than (II) are demonstrated in detail.

  First, a functional group that can be hydrolyzed by an alkaline aqueous solution (developer) having a pH of 10 or more to become an acid group will be described. As such a functional group, what is represented by following General formula (10) is mentioned preferably, and it is preferable to have this in a polymer side chain.

In the general formula (10), Q represents a linking group which links the polymer backbone skeleton and X ^9.
X ⁹ represents a protecting group that is hydrolyzed by an alkaline aqueous solution having a pH of 10 or more. Here, when the functional group represented by the general formula (10) becomes -Q-OH after hydrolysis, -Q-OH represents an acid group having a pKa of 10 or less.
Here, the linking group Q may have a trivalent or higher valent linking group. In that case, the general formula (10) is represented by the following general formula (10 ′). N represents an integer selected from 2 to 5.

Examples of the linking group Q ¹ include those in which the pKa of -Q ¹ -OH can be 10 or less, particularly when the functional group after hydrolysis is -Q ¹ -OH. 10 is preferable. Q ¹ is preferably a hydrocarbon-based linking group, and examples of such hydrocarbon groups include linear, branched, and cyclic alkyl groups, aromatic ring groups, and the like. The pKa of the functional group after hydrolysis can be selected within the above range. Usually, pKa can be made into said range by introduce | transducing an electron-withdrawing substituent into such a bivalent or more valent hydrocarbon group.
Preferable examples of the hydrocarbon group represented by Q ¹ include an aromatic ring group and a cyclo ring group.

X ¹⁰ is not particularly limited as long as it is a functional group that can function as a protective group until it is hydrolyzed and eliminated by an aqueous alkali solution having a pH of 10 or more.
Preferred examples of such X ¹⁰ include substituted oxy groups, substituted thio groups, and substituted amino groups.

  In addition, the functional group according to the present invention is more preferably a functional group represented by the following general formula (11).

A ⁴ represents an aromatic ring group or a cyclo ring group. Specific examples include an aromatic ring group having about 4 to 50 carbon atoms, a heterocyclic group, a condensed polycyclic structure, and an aliphatic cyclic structure.
n represents an integer selected from 1 to 5, and is preferably 1 to 3 from the viewpoint of the balance between alkali solubility in the unexposed area and alkali developability in the exposed area.

X ^{11 is, -NR 27 R 28, -SR 29} , it represents a ^{-OR 30.} Here, R ^{27 to} R ³⁰ each independently represent a substituent composed of one or more atoms selected from the group consisting of a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom. For example, the alkyl group which may have a substituent, the aryl group which may have a substituent, etc. are mentioned.

Examples of the alkyl group represented by R ^{27 to} R ³⁰ include a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms. Specific examples thereof include a methyl group, Ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group, octadecyl group, eicosyl group, isopropyl group, isobutyl group S-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group and 2-norbornyl group. it can. Of these, linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, and cyclic alkyl groups having 5 to 10 carbon atoms are more preferable.

Examples of the substituent that can be introduced into such an alkyl group include a monovalent non-metallic atomic group excluding a hydrogen atom, such as a halogen atom (—F, —Br, —Cl, —I), hydroxyl group Group, alkoxy group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N- Diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkyl Rufoxy group, arylsulfoxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkylureido group, N ′ An arylureido group, an N ′, N′-diarylureido group, an N′-alkyl-N′-arylureido group, an N-alkylureido group, an N-arylureido group, an N′-alkyl-N-alkylureido group, N′-alkyl-N-arylureido group, N ′, N′-dialkyl-N-alkylureido group, N ′, N′-dialkyl-N-arylureido group, N′-aryl-N-alkylureido group, N′-aryl-N-arylureido group, N ′, N′-diaryl-N-alkylureido group, N ′, N′-diaryl-N-arylureido group N′-alkyl-N′-aryl-N-alkylureido group, N′-alkyl-N′-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N— Alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group and the like Conjugated base group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N- Arylcarbamoyl group, alkylsulfuryl Finyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (—SO ₃ H) and its conjugate base group, alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N , N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, N-acylsulfamoyl group and conjugation thereof base groups, N- alkylsulfonylsulfamoyl group (-SO NHSO ₂ (alkyl)) and its conjugated base group, N- aryl sulfonylsulfamoyl group _{(-SO 2 NHSO 2 (aryl)} ) and its conjugated base group, N- alkylsulfonylcarbamoyl group _(-CONHSO 2 _(alkyl)) And its conjugate base group, N-arylsulfonylcarbamoyl group (—CONHSO ₂ (aryl)) and its conjugate base group, alkoxysilyl group (—Si (Oalkyl) ₃ ), aryloxysilyl group (—Si (Oaryl) ₃ ) , Hydroxysilyl group (—Si (OH) ₃ ) and its conjugate base group, phosphono group (—PO ₃ H ₂ ) and its conjugate base group, dialkylphosphono group (—PO ₃ (alkyl) ₂ ), diarylphosphono Group (—PO ₃ (aryl) ₂ ), alkylarylphosphono group (—P O ₃ (alkyl) (aryl)), monoalkylphosphono group (—PO ₃ H (alkyl)) and its conjugate base group, monoarylphosphono group (—PO ₃ H (aryl)) and its conjugate base group, Phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group, dialkylphosphonooxy group (—OPO ₃ (alkyl) ₂ ), diarylphosphonooxy group (—OPO ₃ (aryl) ₂ ), alkylarylphosphonooxy Groups (—OPO ₃ (alkyl) (aryl)), monoalkylphosphonooxy groups (—OPO ₃ H (alkyl)) and their conjugate base groups, monoarylphosphonooxy groups (—OPO ₃ H (aryl)) and its conjugate base group, a cyano group, a nitro group, a dialkyl boryl group (-B _{(alkyl) 2),} Jiariruboriru (-B _{(aryl) 2),} alkyl aryl boryl group (-B (alkyl) (aryl) ), dihydroxy boryl group (-B _{(OH) 2)} and its conjugated base group, an alkyl hydroxy boryl group (-B (alkyl ) (OH)) and its conjugated base group, arylhydroxyboryl group (-B (aryl) (OH)) and its conjugated base group, aryl group, alkenyl group, alkynyl group and the like.

Examples of the aryl group represented by R ^{27 to} R ³⁰ include a benzene ring, a group in which 2 to 3 benzene rings form a condensed ring, a group in which a benzene ring and a 5-membered unsaturated ring form a condensed ring, and the like. Specific examples thereof include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenabutenyl group, a fluorenyl group, and the like. Among these, a phenyl group and a naphthyl group are more preferable.
Examples of the substituent that can be introduced into the aryl group include the alkyl group and the substituent that can be introduced into the alkyl group.

Among such X ¹¹ , particularly preferred examples of the substituted amino group represented by —NR ²⁷ R ²⁸ include acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N ′ -Alkylureido group, N ', N'-dialkylureido group, N'-arylureido group, N', N'-diarylureido group, N'-alkyl-N'-arylureido group, N-alkylureido group, N-arylureido group, N′-alkyl-N-alkylureido group, N′-alkyl-N-arylureido group, N ′, N′-dialkyl-N-alkylureido group, N ′, N′-dialkyl- N-arylureido group, N′-aryl-N-alkylureido group, N′-aryl-N-arylureido group, N ′, N′-diaryl-N-alkylureido group, N ', N'-diaryl-N-arylureido group, N'-alkyl-N'-aryl-N-alkylureido group, N'-alkyl-N'-aryl-N-arylureido group, alkoxycarbonylamino group, Aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group Groups. Examples of the alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group. Further, an acylamino group, N- alkylacylamino group, N- for ^{R 31} of the acyl group ^(R 31 CO-) in the aryl acyl amino group, an alkyl group above, a substituted alkyl group, aryl group and substituted aryl group The ones shown can be mentioned. Of these, more preferred are an N-alkylamino group, an N, N-dialkylamino group, an N-arylamino group, and an acylamino group. Specific examples of preferred substituted amino groups include methylamino group, ethylamino group, diethylamino group, morpholino group, piperidino group, pyrrolidino group, phenylamino group, benzoylamino group, acetylamino group and the like.

Y ⁴ represents a single bond, or —O— or —NR ³² —. Here, R ³² represents a hydrogen atom or a hydrocarbon group having about 1 to 10 carbon atoms. Examples of the hydrocarbon group represented by R ³² include an alkyl group, an aryl group, an alkenyl group, and an alkynyl group.
Specific examples of the alkyl group represented by R ³² include, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, isopropyl group, Isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group, cyclohexyl group, 1-adamantyl group, 2 -A linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms such as a norbornyl group.
Specific examples of the aryl group represented by R ³² are selected from the group consisting of an aryl group having 1 to 10 carbon atoms such as a phenyl group, a naphthyl group, and an indenyl group, a nitrogen atom, an oxygen atom, and a sulfur atom. A heteroaryl group having 1 to 10 carbon atoms containing one hetero atom, for example, a furyl group, a thienyl group, a pyrrolyl group, a pyridyl group, a quinolyl group, and the like can be given.
Specific examples of the alkenyl group represented by R ³² include, for example, a vinyl group, 1-propenyl group, 1-butenyl group, 1-methyl-1-propenyl group, 1-cyclopentenyl group, 1-cyclohexenyl group and the like. And a linear, branched or cyclic alkenyl group having 1 to 10 carbon atoms.
Specific examples of the alkynyl group represented by R ³² include alkynyl groups having 1 to 10 carbon atoms such as ethynyl group, 1-propynyl group, 1-butynyl group and 1-octynyl group.
R ³² may have a substituent, and examples of such a substituent are the same as the substituents that can be introduced into the alkyl groups mentioned as R ^{27 to} R ³⁰ . ^The number of carbon atoms of ^{R 32} is 1 to 10 including the carbon number of the substituent.
Note that such Y ⁴ is preferably an oxygen atom or —NH— because synthesis is easy.

  As a method for introducing such a functional group into a polymer compound, a monomer having an unsaturated bond copolymerizable with the functional group and other copolymerization components in the molecule is used. And a copolymerization method. At this time, if necessary, another monomer having no functional group may be copolymerized. In the present invention, in the polymer compound obtained by the copolymerization, a structural unit composed of such a monomer may be referred to as a “unit”.

  Although the preferable specific example of the unit which has the said functional group is shown below, this invention is not limited to these.

Only one type of unit having the functional group may be contained in the binder polymer, or two or more types may be contained.
Further, the organic polymer binder polymer in the present invention may be a polymer composed only of the unit represented by the general formula (9) and the unit having the functional group. Used in combination with a unit consisting of minutes. The total content of the units having the functional group in the copolymer is appropriately determined depending on the structure, the design of the photosensitive layer, etc., but is preferably 1 to 99 mol%, more preferably 5 based on the total molar amount of the polymer component. It is contained in a range of ˜90 mol%, more preferably 10 to 70 mol%.

  The structural unit having the specific acid group may be contained singly or in combination of two or more in the binder polymer.

  In the organic polymer polymer of the present invention, the content of the acid group having an acid dissociation constant (pKa) of 0 or more and 11 or less, which is an embodiment of (II), is preferably 0.00 per gram of the organic polymer polymer. It is 01-10.0 mmol, More preferably, it is 0.05-7.0 mmol.

  Another preferred embodiment of the binder polymer has an acid group having a pKa of 0 or more and 11 or less, and further has an ethylenically unsaturated double bond (hereinafter referred to as “radical polymerizable group” as appropriate) in its side chain. And an embodiment having the above). The method for introducing a radical polymerizable group into the side chain of the organic polymer in the present invention is represented by the following general formula (A) to the following general formula (E) in addition to the unit having the functional group. The method of combining the unit which has a radically polymerizable group of a structure is mentioned. The content of the radical polymerizable group in the organic polymer (content of unsaturated double bond capable of radical polymerization by iodine titration) is preferably 0.1 to 10.0 mmol per 1 g of the organic polymer. Preferably it is 1.0-8.0 mmol, Most preferably, it is 1.5-7.0 mmol. Moreover, only one type of such units may be contained in the organic polymer, or two or more types may be contained.

First, general formula (A) to general formula (C) will be described.
In general formula (A) to general formula (C), R ^{33 to} R ⁴³ each independently represents a hydrogen atom or a monovalent substituent.
X ¹² and Y ⁵ each independently represent an oxygen atom, a sulfur atom, or —NR ⁴⁴ —.
Z represents an oxygen atom, a sulfur atom, ^{-NR 44} - represents a or a phenylene group.

In the general formula (A), R ^{33 to} R ³⁵ each independently represent a hydrogen atom or a monovalent substituent. Examples of R ³³ include a hydrogen atom or an organic group such as an alkyl group, Specifically, a hydrogen atom, a methyl group, a methylalkoxy group, and a methyl ester group are preferable. R ³⁴ and R ³⁵ 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 alkyl group, an aryl group, or an alkoxy group. , An aryloxy group, an alkylamino group, an arylamino group, an alkylsulfonyl group, an arylsulfonyl group, and the like. Among them, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group, and an aryl group are preferable.
Here, each of the above groups may have a substituent, and examples of the substituent that can be introduced into these groups include a methoxycarbonyl group, an ethoxycarbonyl group, an isopropyloxycarbonyl group, a methyl group, an ethyl group, and a phenyl group. Is mentioned.
X ¹² represents an oxygen atom, a sulfur atom, or —N—R ⁴⁴ , where R ⁴⁴ includes an alkyl group that may have a substituent.

In the general formula (B), R ^{36 to} R ⁴⁰ each independently represent a hydrogen atom or a monovalent substituent.
For example, hydrogen atom, halogen atom, amino group, dialkylamino group, carboxyl group, alkoxycarbonyl group, sulfo group, nitro group, cyano group, alkyl group, aryl group, alkoxy group, aryloxy group, alkylamino group, arylamino Group, an alkylsulfonyl group, an arylsulfonyl group, and the like. Among them, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group, and an aryl group are preferable.
Here, each of the above groups may have a substituent, and examples of the substituent that can be introduced into these groups include those exemplified as the substituent that can be introduced in the general formula (A).
Y ⁵ each independently represents an oxygen atom, a sulfur atom, or —NR ⁴⁴ —. As R ^{44, the same} as in general formula (A) can be mentioned.

In the general formula (C), R ^{41 to} R ⁴³ each independently represents a hydrogen atom or a monovalent substituent. Specifically, for example, a hydrogen atom, a halogen atom, an amino group, or a dialkylamino group Carboxyl group, alkoxycarbonyl group, sulfo group, nitro group, cyano group, alkyl group, aryl group, alkoxy group, aryloxy group, alkylamino group, arylamino group, alkylsulfonyl group, arylsulfonyl group, etc. Of these, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group, and an aryl group are preferable.
Here, each of the above groups may have a substituent, and examples of the substituent that can be introduced into these groups include those exemplified as the substituent that can be introduced in the general formula (A).
Z represents an oxygen atom, a sulfur atom, —N—R ⁴⁴ or a phenylene group. As R ^{44, the same} as in general formula (A) can be mentioned.
Specific examples (1 to 47) preferable as the unit having a radically polymerizable group having a structure represented by the general formulas (A) to (C) are shown below, but the present invention is not limited thereto. Absent.

  The polymer having a radically polymerizable group having a structure represented by the general formula (A) according to the present invention can be produced by at least one of the following synthesis methods (1) and (2).

-Synthesis method (1)-
After synthesizing a polymer compound by polymerizing one or more radically polymerizable compounds represented by the following general formula (a), a proton is extracted using a base, and Z ¹ is eliminated to obtain a desired compound. This is a method for obtaining a polymer compound.

In the general formula ^{(a), R} 33 ~R ³⁵ have the same meanings as ^R 33 ^{to R 35} in the general formula (A).
X ¹³ represents an oxygen atom, a sulfur atom, —NH—, or —NR ⁴⁵ — (wherein R ⁴⁵ represents an alkyl group which may have a substituent).
Z ¹ represents an anionic leaving group.
Q ² represents an oxygen atom, —NH—, or NR ⁴⁶ — (wherein R ⁴⁶ represents an alkyl group which may have a substituent).
R ⁴⁷ includes a hydrogen atom or an alkyl group which may have a substituent, and among them, a hydrogen atom, a methyl group, a methylalkoxy group and a methyl ester group are preferable.
A ⁵ represents a divalent organic linking group.

  Examples of the radical polymerizable compound represented by the general formula (a) include, but are not limited to, the following compounds.

These radically polymerizable compounds represented by the general formula (a) can be easily obtained as a commercial product or by a synthesis method shown in Synthesis Examples described later.
A polymer compound was synthesized by polymerizing by one ordinary radical polymerization method using one or more of these radically polymerizable compounds represented by the general formula (a) and other radically polymerizable compounds as required. Thereafter, a desired amount of a base is dropped into a polymer solution under a cooling or heating condition to perform a reaction, and if necessary, neutralization treatment with an acid is performed to represent the general formula (A). Groups can be introduced. A generally known suspension polymerization method or solution polymerization method can be applied to the production of the polymer compound.
Here, as a base to be used, either an inorganic compound (inorganic base) or an organic compound (organic base) may be used. Preferred inorganic bases include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate and the like, and organic bases include sodium methoxide, sodium ethoxide, potassium tert-butoxide. And metal amine alkoxides, triethylamine, pyridine, and organic amine compounds such as diisopropylethylamine.

-Synthesis method (2)-
After synthesizing a trunk polymer compound (polymer compound constituting the main chain) by using at least one radical polymerizable compound having a functional group, the side chain functional group of the trunk polymer compound and the following general formula In this method, a desired polymer compound is obtained by reacting a compound having the structure represented by (b).

R < ³³ > -R < ³⁵ > in General formula (b) is synonymous with R < ³³ > -R < ³⁵ > in the said general formula (A).

Examples of the functional group of the radical polymerizable compound having a functional group used for the synthesis of the trunk polymer compound in the synthesis method (2) include a hydroxyl group, a carboxyl group, a carboxylic acid halide group, a carboxylic acid anhydride group, an amino group, Examples include halogenated alkyl groups, isocyanate groups, and epoxy groups. Specific examples of the radical polymerizable compound having such a functional group include 2-hydroxylethyl acrylate, 2-hydroxylethyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, acrylic acid, methacrylic acid, acrylic acid chloride, methacrylic acid. Examples include acid chloride, methacrylic anhydride, N, N-dimethyl-2-aminoethyl methacrylate, 2-chloroethyl methacrylate, 2-isocyanate ethyl methacrylate, glycidyl acrylate, and grindyl methacrylate.
After synthesizing one or more radically polymerizable compounds having such a functional group and copolymerizing with other radically polymerizable compounds as necessary to synthesize a trunk polymer compound, the above general formula (b) A desired polymer compound can be obtained by reacting a compound having the group represented.
Here, as an example of the compound having a group represented by the general formula (b), the compounds mentioned as specific examples of the radical polymerizable compound having such a functional group are mentioned.

  The polymer having a radically polymerizable group having a structure represented by the general formula (B) according to the present invention can be produced by at least one of the following synthesis method (3) and synthesis method (4).

-Synthesis method (3)-
One or more radically polymerizable compounds having an unsaturated group represented by the general formula (B) and an ethylenically unsaturated group further rich in addition polymerization than the unsaturated group, and further if necessary A method of polymerizing another radical polymerizable compound to obtain a polymer compound. This method uses a compound having a plurality of ethylenically unsaturated groups having different addition polymerization properties in one molecule, for example, a compound such as allyl methacrylate.

  Examples of the radical polymerizable compound having an ethylenically unsaturated group rich in addition polymerization than the unsaturated group represented by the general formula (B) include allyl acrylate, allyl methacrylate, 2-allyloxyethyl acrylate, 2 Examples include -allyloxyethyl methacrylate, propargyl acrylate, propargyl methacrylate, N-allyl acrylate, N-allyl methacrylate, N, N-diallyl acrylate, N, N-diallyl methacrylamide, allyl acrylamide, and allyl methacrylamide.

-Synthesis method (4)-
After synthesizing one or more radically polymerizable compounds having a functional group to synthesize a polymer compound, a side chain functional group and a compound having a structure represented by the following general formula (c) are reacted to form a general formula (B The method of introduce | transducing group represented by this.

Formula (c) ^R 36 ^{~R 40} in has the same meaning as ^R 36 ^{to R 40} in the general formula (B).

Specific examples of the radical polymerizable compound having a functional group in the synthesis method (4) include specific examples of the radical polymerizable compound having a functional group shown in the synthesis method (2).
Examples of the compound having the structure represented by the general formula (c) include allyl alcohol, allylamine, diallylamine, 2-allyloxyethyl alcohol, 2-chloro-1-butene, and allyl isocyanate.

  The polymer having a radical polymerizable group having a structure represented by the general formula (C) according to the present invention can be produced by any one of the synthesis method (5) and the synthesis method (6) shown below.

-Synthesis method (5)-
One or more radically polymerizable compounds having an unsaturated group represented by the general formula (C) and an ethylenically unsaturated group further rich in addition polymerization than the unsaturated group, and further if necessary A method of obtaining a polymer compound by copolymerizing with another radical polymerizable compound.

  Examples of the radical polymerizable compound having an ethylenically unsaturated group richer in addition polymerization than the unsaturated group represented by the general formula (C) include vinyl acrylate, vinyl methacrylate, 2-phenylvinyl acrylate, 2- Examples include phenyl vinyl methacrylate, 1-propenyl acrylate, 1-propenyl methacrylate, vinyl acrylamide, vinyl methacrylamide and the like.

-Synthesis method (6)-
A method in which one or more radically polymerizable compounds having a functional group are polymerized to synthesize a polymer compound, and then a side chain functional group and a compound having a structure represented by the general formula (d) are reacted and introduced.

^R 41 ^{to R} in the general formula (d) ⁴³ has the same meaning as ^R 41 ^{to R 43} in the general formula (C).

Specific examples of the radical polymerizable compound having a functional group in the synthesis method (6) include specific examples of the radical polymerizable compound having a functional group shown in the synthesis method (2).
Examples of the compound having the structure represented by the general formula (d) include 2-hydroxyethyl monovinyl ether, 4-hydroxybutyl monovinyl ether, diethylene glycol monovinyl ether, 4-chloromethylstyrene and the like.

  As described above, the synthesis method (1) to the synthesis method (6) of the polymer having a radical polymerizable group having a structure represented by the general formula (A) to the general formula (C) according to the present invention have been described. In order to synthesize the specific binder polymer in the present invention using a synthesis method, when the radical polymerizable compound is polymerized in each of the synthesis methods (1) to (6), the radical polymerizable compound and the general This is achieved by copolymerizing the unit represented by the formula (9) at a predetermined ratio.

Next, general formula (D) and general formula (E) will be described.
In the general formula (D), R ⁴⁸ represents a hydrogen atom or a methyl group. R ⁴⁹ represents any substitutable atom or atomic group. k represents an integer of 0 to 4. In addition, the radically polymerizable group represented by the general formula (D) is bonded to the polymer main chain through a single bond or a linking group composed of an arbitrary atom or atomic group. There is no limit.

In the general formula (E), R ⁵⁰ represents hydrogen or a methyl group. R ⁵¹ represents any substitutable atom or atomic group. m represents an integer of 0 to 4. A ^- represents an anion. Such a pyridinium ring may take the form of a benzopyridinium fused with a benzene ring as a substituent, and in this case, includes a quinolium group and an isoquinolium group. In addition, the radically polymerizable group represented by the general formula (E) is bonded to the polymer main chain through a single bond or a linking group composed of an arbitrary atom or atomic group, and the bonding method is also particularly preferable. There is no limit.

  Hereinafter, preferred examples of the unit (repeating unit) containing the radically polymerizable group represented by the general formula (D) and the general formula (E) will be shown, but the present invention is not limited thereto.

As described above, among the radical polymerizable groups represented by the general formula (A) to the general formula (E), the radical polymerizable group having a structure represented by the general formula (A) and the general formula (B). It is preferable. Among them, particularly preferred is a radical polymerizable group having a structure represented by the general formula (A), and further, R ^{33 in the} general formula (A) is a hydrogen atom or a methyl group, and X ¹² is an oxygen atom or Most preferred is a nitrogen atom.

  Furthermore, the organic polymer binder polymer in the present invention may be copolymerized with the following components in addition to the unit having the carboxylic acid group and the unit having the radical polymerizable group which is a preferred embodiment. As such a copolymer component, any conventionally known monomer can be used without limitation as long as it is a monomer capable of radical polymerization. Specific examples include monomers described in “Polymer Data Handbook—Basic Edition” (Edition of Polymer Society, Bafukan, 1986). One type of such copolymerization component may be used, or two or more types may be used in combination.

Among these, particularly preferred copolymer components include monomers having the following radical polymerizable groups.
For example, radically polymerizable compounds selected from acrylic acid esters, methacrylic acid esters, N, N-2 substituted acrylamides, N, N-2 substituted methacrylamides, styrenes, acrylonitriles, methacrylonitriles, etc. Can be mentioned.

  Specifically, for example, acrylic esters such as alkyl acrylate (the alkyl group preferably has 1 to 20 carbon atoms) (specifically, for example, methyl acrylate, ethyl acrylate, acrylic Propyl acrylate, butyl acrylate, amyl acrylate, ethyl hexyl acrylate, octyl acrylate, tert-octyl acrylate, chloroethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane Monoacrylate, pentaerythritol monoacrylate, glycidyl acrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, etc.), aryl acrylate (for example, Methacrylic acid esters (e.g., methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate, hexyl methacrylate, Cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, Glycidyl methacrylate, furfuryl methacrylate, tetrahydroph Furyl methacrylate, etc.), aryl methacrylate (eg, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, etc.), for example, styrenes such as styrene, alkylstyrene, etc. (eg, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene) , Isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene, acetoxymethyl styrene, etc.), alkoxy styrene (for example, methoxy styrene, 4- Methoxy-3-methylstyrene, dimethoxystyrene, etc.), halogen styrene (for example, chlorostyrene, dichlorostyrene) Len, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoro Methyl styrene), acrylonitrile, methacrylonitrile and the like.

Of these radical polymerizable compounds, acrylic acid esters, methacrylic acid esters, and styrenes are preferably used.
These radically polymerizable compounds can be used alone or in combination of two or more.

  The most preferable embodiment as the binder polymer in the present invention is a case where the specific radical polymerizable group is included together with the carboxylic acid group represented by the general formula (9).

  Specific examples of the binder polymer in the present invention include those having the radical polymerizable group (i-1) to (i-46) and those having no radical polymerizable group (ii-1) to ( It is divided into ii-5) and indicated by the molar ratio between the structural unit and each structural unit. Mw represents an average molecular weight. However, the present invention is not limited to these.

The molecular weight of the binder polymer in the present invention is appropriately determined from the viewpoints of image formability and printing durability when these are used as components of the photosensitive layer of a lithographic printing plate precursor. Usually, when the molecular weight increases, the printing durability is excellent, but the image formability tends to deteriorate. On the other hand, if it is low, the image forming property is improved, but the printing durability is lowered. The molecular weight of the organic polymer is preferably in the range of 400 to 6,000,000 in terms of weight average molecular weight, and more preferably in the range of 900 to 600,000.
Further, the content of the binder polymer in the present invention is preferably 20 to 80% by mass with respect to the total mass of all solid components constituting the photosensitive layer, from the viewpoints of printing durability and image formability. More preferably, it is -70 mass%.

((B) Compound having ethylenically unsaturated bond capable of addition polymerization)
In the present invention, (B) a compound having an addition-polymerizable ethylenically unsaturated bond (hereinafter referred to as “component (B)” as appropriate) is an addition-polymerizable compound having at least one ethylenically unsaturated double bond. The compound is selected from compounds having at least one, preferably two or more terminal ethylenically unsaturated bonds. Such compound groups are widely known in the industrial field, and these can be used without any particular limitation in the present invention. These have chemical forms such as monomers, prepolymers, i.e. dimers, trimers and oligomers, or mixtures thereof and copolymers thereof. Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, amino group or mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or Also suitable are substitution reaction products of unsaturated carboxylic acid esters or amides having a leaving substituent such as a tosyloxy group with monofunctional or polyfunctional alcohols, amines or thiols. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

  Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate , Tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate , Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer.

  Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy- 2-hydroxypro ) Phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

  Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate.

  Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate.

  Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.

  Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  Examples of other esters include aliphatic alcohol esters described in JP-B-46-27926, JP-B-51-47334, JP-A-57-196231, and JP-A-59-5240. Those having an aromatic skeleton described in JP-A-59-5241, JP-A-2-226149, and those containing an amino group described in JP-A-1-165613 are also preferably used. Furthermore, the ester monomers described above can also be used as a mixture.

  Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like.

  Examples of other preferable amide-based monomers include those having a cyclohexylene structure described in JP-B No. 54-21726.

  In addition, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable, and specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinyl urethane containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (i) to a polyisocyanate compound having two or more isocyanate groups. Compounds and the like.

（ただし、一般式（ｉ）中、Ｒ^５１及びＲ^５２は、ＨまたはＣＨ_３を示す。）

(However, in General Formula (i), R ⁵¹ and R ⁵² represent H or CH _3. )

  Also, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-B-58-49860, JP-B-56- Urethane compounds having an ethylene oxide skeleton described in Japanese Patent No. 17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418 are also suitable.

  Furthermore, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are used. Depending on the case, it is possible to obtain a photopolymerizable composition excellent in the photosensitive speed.

  Other examples include polyester acrylates, epoxy resins and (meth) acrylic acid as described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, and JP-A-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as reacted epoxy acrylates. Further, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337, JP-B-1-40336, and vinylphosphonic acid compounds described in JP-A-2-25493 are also included. be able to. In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

  About these (B) components, the detail of usage methods, such as the structure, single use, combined use, and addition amount, can be arbitrarily set according to the performance design of final polymerizable composition. For example, when the component (B) in the present invention is used as a photosensitive layer of a negative lithographic printing plate precursor, it is selected from the following viewpoints. From the viewpoint of photosensitive speed, a structure having a high unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, in order to increase the strength of the image portion, that is, the cured film, those having three or more functionalities are preferable, and furthermore, different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrenic compound, vinyl ether type). A method of adjusting both photosensitivity and intensity by using a compound) is also effective. A compound having a large molecular weight or a compound having high hydrophobicity is excellent in photosensitive speed and film strength, but is not preferable in terms of development speed and precipitation in a developer. Also, for compatibility with other components in the photosensitive layer (for example, binder polymer such as component (A), light or thermal polymerization initiator (C) component, colorant, etc.), dispersibility, The selection and use method of the addition polymerization compound is an important factor. For example, the compatibility may be improved by using a low-purity compound or using two or more kinds in combination.

  In addition, when the polymerizable composition in the present invention is applied as a photosensitive layer of a lithographic printing plate precursor, a specific structure is selected for the purpose of improving the adhesion of the support of the lithographic printing plate precursor or a protective layer described later. It is possible to do. With regard to the blending ratio of the component (B) in the photosensitive layer, a larger amount is more advantageous in terms of sensitivity. For example, problems such as transfer of photosensitive layer components and manufacturing defects due to adhesion) and precipitation from a developer may occur. From these viewpoints, the component (B) is preferably used in the range of 5 to 80% by mass, and more preferably 25 to 75% by mass with respect to the nonvolatile component in the photosensitive layer. These may be used alone or in combination of two or more. In addition, the component (B) can be arbitrarily selected according to an appropriate structure, blending, and addition amount from the viewpoint of polymerization inhibition with respect to oxygen, resolution, fogging, refractive index change, surface adhesiveness, and the like. Can also be used for the layer construction and coating method such as the undercoat layer below.

((C) photo or thermal polymerization initiator)
As the photopolymerization initiator in the present invention, various photopolymerization initiators known in patents, literatures, etc., or a combination system of two or more photopolymerization initiators (photopolymerization initiation system) depending on the wavelength of the light source used. Can be appropriately selected and used.

  In the case of using a blue semiconductor laser, Ar laser, second harmonic of an infrared semiconductor laser, or SHG-YAG laser as a light source, various photopolymerization initiators (systems) have been proposed. Certain photoreducible dyes described in the specification of 850,445, such as rose bengal, eosin, erythrosine, etc., or a combination of a dye and an initiator, such as a complex initiator system of a dye and an amine (Japanese Patent Publication No. 44) -20099), a combination system of hexaarylbiimidazole, a radical generator and a dye (Japanese Patent Publication No. 45-37377), a system of hexaarylbiimidazole and p-dialkylaminobenzylidene ketone (Japanese Patent Publication No. 47-2528). JP, 54-155292, cyclic cis-α-dicarbonyl compound and dye system (JP 48) 84183), a system of cyclic triazine and a merocyanine dye (Japanese Patent Laid-Open No. 54-151024), a system of 3-ketocoumarin and an activator (Japanese Patent Laid-Open No. 52-112682, Japanese Patent Laid-Open No. 58-15503). , Biimidazole, styrene derivative, thiol system (JP 59-140203 A), organic peroxide and dye system (JP 59-1504 A, JP 59-140203 JP, JP JP-A 59-189340, JP-A 62-174203, JP-B 62-1641, US Pat. No. 4,766,055), a system of dye and active halogen compound (JP-A 63-1718105, JP-A-63-258903, JP-A-3-264771, etc.), a system of a dye and a borate compound (JP-A-62-143044) JP-A-62-15242, JP-A-64-13140, JP-A-64-13141, JP-A-64-13142, JP-A-64-13143, JP-A-64-64. No. 13144, JP-A 64-17048, JP-A 1-222903, JP-A 1-298348, JP-A 1-138204, etc.), a dye having a rhodanine ring and a radical generator System (JP-A-2-179433, JP-A-2-244050), titanocene and 3-ketocoumarin dye system (JP-A 63-221110), titanocene and xanthene dye, further containing amino group or urethane group Combinations of ethylenically unsaturated compounds capable of addition polymerization (JP-A-4-221958, JP-A-4-219756) , Titanocene and systems (JP-A-6-295061) a specific merocyanine dye, a dye system with titanocene and benzopyran ring (JP-A-8-334897 JP), and the like.

  In the present invention, a particularly preferred photopolymerization initiator (system) contains at least one titanocene. The titanocene compound used as a photopolymerizable initiator (system) in the present invention may be any titanocene compound that can generate an active radical when irradiated with light in the presence of other sensitizing dyes. For example, JP 59-152396 A, JP 61-151197 A, JP 63-41483 A, JP 63-41484 A, JP 2-249 A, and JP 2 -291, JP-A-3-27393, JP-A-3-12403, and JP-A-6-41170 can be appropriately selected and used.

  More specifically, di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,3,4,5 , 6-pentafluorophen-1-yl (hereinafter also referred to as “T-1”), di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di- -Cyclopentadienyl-Ti-bis-2,4,6-trifluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, di-cyclo Pentadienyl-Ti-bis-2,4-difluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl Di-methylcyclopentadie Ru-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4-difluorophen-1-yl, bis (cyclo And pentadienyl) -bis (2,6-difluoro-3- (pyr-1-yl) phenyl) titanium (hereinafter also referred to as “T-2”).

  These titanocene compounds can be further subjected to various chemical modifications for improving the characteristics of the photosensitive layer. For example, bonding with sensitizing dyes, addition polymerizable unsaturated compounds and other radical generating parts, introduction of hydrophilic sites, compatibility improvement, introduction of substituents to suppress crystal precipitation, introduction of substituents to improve adhesion A method such as polymerization can be used.

  The use method of these titanocene compounds can be arbitrarily set as appropriate depending on the performance design of the polymerizable composition and the later-described lithographic printing plate precursor to which the polymerizable composition is applied, like the above-described addition polymerizable compound. For example, when applied to the photosensitive layer of a lithographic printing plate precursor, compatibility with the photosensitive layer can be enhanced by using two or more types in combination. The amount of photopolymerization initiator such as the titanocene compound used is usually more advantageous in terms of photosensitivity, and the content in the polymerizable composition is the same when used in the photosensitive layer of a lithographic printing plate precursor. For 100 parts by mass of the non-volatile component, 0. Sufficient photosensitivity is obtained by using in 5-80 mass parts, Preferably it is 1-50 mass parts. On the other hand, when used under yellow light or white light, the amount of titanocene used is preferably small in terms of fogging by light at around 500 nm, but the amount of titanocene used is 6 in combination with other sensitizing dyes. Sufficient photosensitivity can be obtained even if it is lowered to not more than parts by mass, further not more than 1.9 parts by mass, and further not more than 1.4 parts by mass.

As the thermal polymerization initiator for initiating and advancing the polymerization of the component (B) used in the present invention, a thermal decomposition type radical generator that decomposes by heat to generate radicals is useful. Such radical generators are used in combination with an infrared absorbing dye, which will be described later, so that when the infrared laser is irradiated, the infrared absorbing dye generates heat and generates radicals by the heat. Recording is possible with these combinations. It becomes.
Examples of the radical generator include onium salts, triazine compounds having a trihalomethyl group, peroxides, azo polymerization initiators, azide compounds, quinonediazides, oxime ester compounds, triaryl monoalkylborate compounds, etc. Or an oxime ester compound has high sensitivity and is preferable. Below, the onium salt which can be used suitably as a polymerization initiator in this invention is demonstrated. Preferred onium salts include iodonium salts, diazonium salts, and sulfonium salts. In the present invention, these onium salts function not as acid generators but as radical polymerization initiators. The onium salt suitably used in the present invention is an onium salt represented by the following general formulas (F) to (H).

In general formula (F), Ar ¹¹ and Ar ¹² each independently represents an aryl group having 20 or less carbon atoms, which may have a substituent. Preferred substituents when this aryl group has a substituent include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, or a carbon atom having 12 or less carbon atoms. An aryloxy group is mentioned.
Z ¹¹⁻ represents a counter ion selected from the group consisting of a halogen ion, a perchlorate ion, a tetrafluoroborate ion, a hexafluorophosphate ion, a carboxylate ion, and a sulfonate ion, preferably a perchlorate ion, Hexafluorophosphate ions, carboxylate ions, and aryl sulfonate ions.

In the general formula (G), Ar ²¹ represents an aryl group having 20 or less carbon atoms which may have a substituent. Preferred examples of the substituent include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, an aryloxy group having 12 or less carbon atoms, and 12 or less carbon atoms. Examples thereof include an alkylamino group, a dialkylamino group having 12 or less carbon atoms, an arylamino group having 12 or less carbon atoms, or a diarylamino group having 12 or less carbon atoms.
Z ^21- represents a counter ion having the same ^meaning as Z ^11- .

In general formula (H), R ⁵³ , R ⁵⁴ and R ⁵⁵ may be the same or different and each represents a hydrocarbon group having 20 or less carbon atoms which may have a substituent. Preferred substituents include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, or an aryloxy group having 12 or less carbon atoms.
Z ^31- represents a counter ion having the same ^meaning as Z ^11- .

  In the present invention, specific examples of onium salts that can be suitably used as a polymerization initiator (radical generator) include those described in JP-A-2001-133696. In the present invention, onium salts represented by general formula (F) ([OI-1] to [OI-10]) and onium salts represented by general formula (G) ([ON] which can be suitably used in the present invention are shown below. -1] to [ON-5]), and specific examples of the onium salts ([OS-1] to [OS-7]) represented by the general formula (H), are not limited thereto. .

  The polymerization initiator used in the present invention preferably has a maximum absorption wavelength of 400 nm or less, and more preferably 360 nm or less. By making the absorption wavelength in the ultraviolet region in this way, the lithographic printing plate precursor can be handled under white light.

Other preferable polymerization initiators include specific aromatic sulfonium salts described in Japanese Patent Application No. 2000-266797, Japanese Patent Application No. 2001-177150, Japanese Patent Application No. 2000-160323, and Japanese Patent Application No. 2000-184603. The typical compound is illustrated below.
In addition, typical compounds of other preferable polymerization initiators that can be applied to the present invention are exemplified below.

  Moreover, the oxime ester compound which can be used suitably as a polymerization initiator in this invention is demonstrated below. Preferred oxime ester compounds include those represented by the following general formula (I).

In the general formula (I), X ¹⁴ represents a carbonyl group, a sulfone group, or a sulfoxide group, and Y ⁵ represents a cyclic or chain alkyl group having 1 to 12 carbon atoms, an alkenyl group, an alkynyl group, or a C 6-18 carbon atom. An aryl group and a heterocyclic group, and the aryl group is an aromatic hydrocarbon compound such as a benzene ring, naphthalene ring, anthracene ring, phenanthrene group, pyrene group, triphenylene group, and the heterocyclic ring is a nitrogen atom, a sulfur atom, An aromatic compound having at least one oxygen atom in the ring structure, for example, pyrrole group, furan group, thiophene group, selenophene group, pyrazole group, imidazole group, triazole group, tetrazole group, oxazole group, thiazole group, indole Group, benzofuran group, benzimidazole group, benzoxazole group, benzothiazole group, pyri Down group, a pyrimidine group, a pyrazine group, a triazine group, a quinoline group, a carbazole group, an acridine group, a phenoxazine, and a compound such as phenothiazine.
These substituents represented by Y ⁵ are halogen atoms, hydroxyl groups, nitrile groups, nitro groups, carboxyl groups, aldehyde groups, alkyl groups, thiol groups, aryl groups, or alkenyl groups, alkynyl groups, ether groups, ester groups, Urea group, amino group, amide group, sulfide group, disulfide group, sulfoxide group, sulfo group, sulfone group, hydrazine group, carbonyl group, imino group, halogen atom, hydroxyl group, nitrile group, nitro group, carboxyl group, carbonyl group, It can be substituted by a compound containing a urethane group, an alkyl group, a thiol group, an aryl group, a phosphoroso group, a phospho group, or a carbonyl ether group.

Z ² in the general formula (I) is synonymous with Y ⁵ or is a nitrile group, a halogen atom, a hydrogen atom, or an amino group, and these compounds of Z ² are a halogen atom, a hydroxyl group, a nitrile group, a nitro group, and a carboxyl group. Aldehyde group, alkyl group, thiol group, aryl group or alkenyl group, alkynyl group, ether group, ester group, urea group, amino group, amide group, sulfide group, disulfide group, sulfoxide group, sulfo group, sulfone group, hydrazine Group, carbonyl group, imino group, halogen atom, hydroxyl group, nitrile group, nitro group, carboxyl group, carbonyl group, urethane group, alkyl group, thiol group, aryl group, phosphoroso group, phospho group, carbonyl ether group Can be replaced.

W in the general formula (I) represents a divalent organic group, and represents a methylene group, a carbonyl group, a sulfoxide group, a sulfone group, or an imino group. The methylene group and imino group are an alkyl group, an aryl group, an ester group, and a nitrile. It can be substituted by a compound containing a group, a carbonyl ether group, a sulfo group, a sulfo ether group, an ether group or the like.
n represents an integer of 0 or 1.

V in the general formula (I) is a C1-C12 cyclic or chain alkyl group, alkenyl group, alkynyl group, C6-C18 aryl group, alkoxy group or aryloxy group. Aromatic hydrocarbon compounds such as benzene ring, naphthalene ring, anthracene ring, phenanthrene group, pyrene group, triphenylene group, pyrrole group, furan group, thiophene group, selenophene group, pyrazole group, imidazole group, triazole group, tetrazole group, oxazole Group, thiazole group, indole group, benzofuran group, benzimidazole group, benzoxazole group, benzothiazole group, pyridine group, pyrimidine group, pyrazine group, triazine group, quinoline group, carbazole group, acridine group, phenoxazine, phenothiazine, etc. Heteroatom containing Aromatic compounds and the like. These V compounds are halogen atoms, hydroxyl groups, nitrile groups, nitro groups, carboxyl groups, aldehyde groups, alkyl groups, thiol groups, aryl groups or alkenyl groups, alkynyl groups, ether groups, ester groups, urea groups, amino groups, amides. Group, sulfide group, disulfide group, sulfoxide group, sulfo group, sulfone group, hydrazine group, carbonyl group, imino group, halogen atom, hydroxyl group, nitrile group, nitro group, carboxyl group, carbonyl group, urethane group, alkyl group, thiol It can be substituted by a compound containing a group, an aryl group, a phosphoroso group, a phospho group, or a carbonyl ether group.
V and Z may be bonded to each other to form a ring.

As the oxime ester compound represented by the general formula (I), from the viewpoint of sensitivity, X ¹⁴ is carbonyl, Y ⁵ is an aryl group or benzoyl group, Z is an alkyl group or aryl group, W is a carbonyl group, V is preferably an aryl group. More preferably, the aryl group of V has a thioether substituent.
The structure of the N—O bond in the general formula (I) may be E-form or Z-form.

  Other oxime ester compounds that can be suitably used in the present invention include Progress in Organic Coatings, 13 (1985) 123-150; C. S Perkin II (1979) 1653-1660; Journal of Photopolymer Science and Technology (1995) 205-232; C. S Perkin II (1979) 156-162; JP-A 2000-66385; JP-A 2000-80068.

  Although the specific example of the oxime ester compound which can be used suitably for this invention is shown below, it is not limited to this.

  In the present invention, it is more preferable to use a titanocene compound, a sulfonium compound, or a hexaarylbiimidazole compound among the above polymerization initiators from the viewpoint of polymerization initiation efficiency during exposure, and even more preferable to use a hexaarylbiimidazole compound. .

  These polymerization initiators are, for example, polymerizable from the viewpoint of the sensitivity when the polymerizable composition of the present invention is applied as a photosensitive layer of a negative lithographic printing plate precursor, and the stain resistance of non-image areas generated during printing. The total solid content constituting the composition or the photosensitive layer can be added in an amount of 0.1 to 50% by mass, preferably 0.5 to 30% by mass, and particularly preferably 1 to 20% by mass. These polymerization initiators may be used alone or in combination of two or more. Moreover, these polymerization initiators may be added to the same layer as other components, or another layer may be provided and added thereto.

From the viewpoint of improving the sensitivity of the polymerization initiator, (D) a sensitizing dye or (D ′) an infrared absorbing dye can be used for the photosensitive layer in the present invention depending on the wavelength of the laser at the time of exposure. Specific description will be given below.
[(D) Sensitizing dye]
When the electromagnetic wave used for polymerization is ultraviolet light or visible light, it preferably contains a sensitizing dye having a maximum absorption wavelength at about 300 nm to 850 nm, and more preferably has an absorption peak at 350 nm to 450 nm. Examples of such sensitizing dyes include spectral sensitizing dyes and the following dyes or pigments that absorb light from a light source and interact with a photopolymerization initiator.
Preferred spectral sensitizing dyes or dyes include polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, thianes). Carbocyanine, oxacarbocyanine), merocyanines (eg merocyanine, carbomerocyanine), thiazines (eg thioene, methylene blue, toluidine blue), acridines (eg acridine orange, chloroflavin, acriflavine), phthalocyanines (For example, phthalocyanine, metal phthalocyanine), porphyrins (for example, tetraphenylporphyrin, central metal-substituted porphyrin), chlorophylls (for example, chlorophyll, chlorophyllin, central gold) Substituted chlorophyll), metal complexes, anthraquinones (e.g., anthraquinone), squarylium compound (e.g., squarylium), and the like.

  Examples of more preferable spectral sensitizing dyes or dyes include styryl dyes described in JP-B-37-13034, cationic dyes described in JP-A-62-143044, and quinoxalinium described in JP-B-59-24147. Salts, new methylene blue compounds described in JP-A No. 64-33104, anthraquinones described in JP-A No. 64-56767, benzoxanthene dyes described in JP-A No. 2-1714, JP-A No. 2-226148 and Acridines described in JP-A-2-226149, pyrylium salts described in JP-B-40-28499, cyanines described in JP-B-46-42363, benzofuran dyes described in JP-A-2-63053, Conjugated ketone dyes described in Kaihei 2-85858 and JP-A-2-216154 No. 57-10605, dyes described in JP-B-2-30321, azocinnamilidene derivatives, cyanine dyes described in JP-A-1-287105, JP-A-62-31844, JP-A-62-2 No. 31848, xanthene dyes described in JP-A-62-143043, aminostyryl ketones described in JP-B-59-28325, merocyanine dyes described in JP-B-61-9621, and JP-A-2-179634 Described, merocyanine dye described in JP-A-2-244050, merocyanine dye described in JP-B-59-28326, merocyanine dye described in JP-A-59-89803, merocyanine described in JP-A-8-129257 Dyes, benzopyran dyes described in JP-A-8-334897, etc. It can be.

  The sensitizing dye used in the present invention is more preferably one represented by the following general formula (12).

In General Formula (12), A ⁶ represents an aromatic ring or a hetero ring which may have a substituent, X ¹⁵ represents an oxygen atom or a sulfur atom or —N (R ⁵⁶ ) —, and Y ⁶ represents oxygen. It represents an atom or -N ( ^R56 )-.
R ⁵⁶ , R ⁵⁷ and R ⁵⁸ each independently represent a hydrogen atom or a monovalent non-metallic atomic group, and A ⁶ and R ⁵⁶ , R ⁵⁷ and R ⁵⁸ are bonded to each other to form an aliphatic group. Or aromatic rings can be formed.

Here, when R ⁵⁶ , R ⁵⁷ and R ⁵⁸ represent a monovalent nonmetallic atomic group, they preferably represent a substituted or unsubstituted alkyl group or aryl group.
Next, preferred examples of R ⁵⁶ , R ⁵⁷ and R ⁵⁸ will be specifically described. Examples of preferable alkyl groups include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, Butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, s-butyl, Examples thereof include t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group and 2-norbornyl group. Of these, linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, and cyclic alkyl groups having 5 to 10 carbon atoms are more preferable.

As the substituent of the substituted alkyl group, a monovalent non-metallic atomic group other than hydrogen is used. Preferred examples include halogen atoms (—F, —Br, —Cl, —I), hydroxyl groups, alkoxy groups. Group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diaryl Amino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy Group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy , Arylsulfoxy group, acyloxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkylureido group, N '-Arylureido group, N', N'-diarylureido group, N'-alkyl-N'-arylureido group, N-alkylureido group, N-arylureido group, N'-alkyl-N-alkylureido group N′-alkyl-N-arylureido group, N ′, N′-dialkyl-N-alkylureido group, N ′, N′-dialkyl-N-arylureido group, N′-aryl-N-alkylureido group N′-aryl-N-arylureido group, N ′, N′-diaryl-N-alkylureido group, N ′, N′-diaryl-N-aryluree Id group, N′-alkyl-N′-aryl-N-alkylureido group, N′-alkyl-N′-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl- N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group , Alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group An alkylsulfinyl group, Arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (—SO ₃ H) and its conjugate base group (hereinafter referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkyls Rufinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkyl Sulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group (—PO ₃ H ₂₎ and its conjugated base group (hereinafter referred to as phosphonato group) Dialkylphosphono group _{(-PO 3 (alkyl) 2)} , diaryl phosphono group _{(-PO 3 (aryl) 2)} , alkyl aryl phosphono group _{(-PO 3 (alkyl) (aryl} )), monoalkyl phosphono group (—PO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkylphosphonate group), monoarylphosphono group (—PO ₃ H (aryl)) and its conjugate base group (hereinafter referred to as arylphosphonate) Group), a phosphonooxy group (—OPO ₃ H ₂ ) and its conjugated base group (hereinafter referred to as phosphonatoxy group), a dialkylphosphonooxy group (—OPO ₃ (alkyl) ₂ ), a diarylphosphonooxy group (— OPO _{3 (aryl) 2),} alkylaryl phosphono group _{(-OPO 3 (alkyl) (aryl} ) , Monoalkyl phosphono group _(-OPO 3 H (alkyl)) and its conjugated base group (hereinafter referred to as alkylphosphonato group), monoarylphosphono group _(-OPO 3 H (aryl)) and its Examples thereof include a conjugated base group (hereinafter referred to as arylphosphonatoxy group), a cyano group, a nitro group, an aryl group, a heteroaryl group, an alkenyl group, an alkynyl group, and a silyl group.
Specific examples of the alkyl group in these substituents include the aforementioned alkyl groups, which may further have a substituent.

  Specific examples of the aryl group include phenyl group, biphenyl group, naphthyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group. , Ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl Group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, phenyl group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophene Group, can be exemplified phosphonophenyl phenyl group.

  As the heteroaryl group, a group derived from a monocyclic or polycyclic aromatic ring containing at least one of nitrogen, oxygen and sulfur atoms is used, and as a particularly preferred example of the heteroaryl ring in the heteroaryl group, Is, for example, thiophene, thiathrene, furan, pyran, isobenzofuran, chromene, xanthene, phenoxazine, pyrrole, pyrazole, isothiazole, isoxazole, pyrazine, pyrimidine, pyridazine, indolizine, isoindolizine, indolizine, indazole, indazole, Purine, quinolidine, isoquinoline, phthalazine, naphthyridine, quinazoline, cinolin, pteridine, carbazole, carboline, phenanthrine, acridine, perimidine, phenanthrolin, phthalazine, phenalazine, phenoxazine, fura Emissions, and the like. These further may be benzo-fused or may have a substituent.

Examples of alkenyl groups include vinyl, 1-propenyl, 1-butenyl, cinnamyl, 2-chloro-1-ethenyl, etc. Examples of alkynyl include ethynyl, 1 -Propynyl group, 1-butynyl group, trimethylsilylethynyl group and the like. Examples of G ¹ in the acyl group (G ¹ CO—) include hydrogen and the above alkyl groups and aryl groups. Among these substituents, even more preferred are halogen atoms (—F, —Br, —Cl, —I), alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, N-alkylamino groups, N, N— Dialkylamino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonate group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group Group, N-arylsulfide Moyl group, N-alkyl-N-arylsulfamoyl group, phosphono group, phosphonate group, dialkyl phosphono group, diaryl phosphono group, monoalkyl phosphono group, alkyl phosphonate group, monoaryl phosphono group, aryl phosphine group Examples include an onato group, a phosphonooxy group, a phosphonateoxy group, an aryl group, an alkenyl group, and an alkylidene group (such as a methylene group).

  On the other hand, examples of the alkylene group in the substituted alkyl group include divalent organic residues obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. Can include linear alkylene groups having 1 to 12 carbon atoms, branched chains having 3 to 12 carbon atoms, and cyclic alkylene groups having 5 to 10 carbon atoms.

Specific examples of preferred substituted alkyl groups as R ¹ , R ² , or R ³ obtained by combining the above substituents and alkylene groups include chloromethyl group, bromomethyl group, 2-chloroethyl group, trifluoromethyl group, methoxy Methyl group, methoxyethoxyethyl group, allyloxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N -Cyclohexylcarbamoyloxyethyl group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxy Carbonylethyl group, allyloxycarbonylbutyl group, chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl -N- (sulfophenyl) carbamoylmethyl group, sulfobutyl group, sulfonatopropyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N- Tolylsulfamoylpropyl group, N-methyl-N- (phosphonophenyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobu Tyl group, methylphosphonatobutyl group, tolylphosphonohexyl group, tolylphosphonatohexyl group, phosphonooxypropyl group, phosphonatoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1 -Phenylethyl group, p-methylbenzyl group, cinnamyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, etc. can be mentioned.

Specific examples of preferred aryl groups as R ⁵⁶ , R ⁵⁷ , or R ⁵⁸ include those in which 1 to 3 benzene rings form a condensed ring, and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring Specific examples include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group. Among these, a phenyl group and a naphthyl group are more preferable. preferable.

Specific examples of the preferable substituted aryl group as R ⁵⁶ , R ⁵⁷ , or R ⁵⁸ include a monovalent nonmetallic atomic group (other than a hydrogen atom) as a substituent on the ring-forming carbon atom of the aryl group. What has is used. Examples of preferred substituents include the alkyl groups, substituted alkyl groups, and those previously shown as substituents in the substituted alkyl group. Preferred examples of such a substituted aryl group include biphenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, fluorophenyl group, chloromethylphenyl group, trifluoromethylphenyl group. Hydroxyphenyl group, methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, Benzoyloxyphenyl group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, cal Xiphenyl group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenylphosphoro Phenyl group, methylphosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonatophenyl group, allylphenyl group, 1-propenylmethylphenyl group, 2-butenylphenyl group, 2-methylallylphenyl Group, 2-methylpropenylphenyl group, 2-propynylphenyl group, 2-butynylphenyl group, 3-butynylphenyl group, and the like.

In addition, more preferable examples of R ⁵⁷ and R ⁵⁸ include substituted or unsubstituted alkyl groups. A more preferred example of R ⁵⁶ is a substituted or unsubstituted aryl group. The reason for this is not clear, but by having such a substituent, the interaction between the electronically excited state caused by light absorption and the initiator compound becomes particularly large, generating radicals, acids or bases of the initiator compound. It is estimated that the efficiency is improved.

Next, ^{A 6} will be described in the general formula (12). A ⁶ represents an aromatic ring or a hetero ring which may have a substituent. Specific examples of the aromatic ring or hetero ring which may have a substituent include R ⁵⁶ and R in the general formula (12). ⁵⁷ or the same as those exemplified in the above description of R ⁵⁸ .
Of these, preferable A ⁶ includes an alkoxy group, a thioalkyl group, and an aryl group having an amino group, and particularly preferable A ⁶ includes an aryl group having an amino group.

Next, Y ⁶ in the general formula (12) will be described. Y ⁶ represents a nonmetallic atomic group necessary for forming a heterocyclic ring in cooperation with the above-described A ⁶ and an adjacent carbon atom. Examples of such a heterocyclic ring include 5-, 6-, and 7-membered nitrogen-containing or sulfur-containing heterocyclic rings that may have a condensed ring, and preferably 5- or 6-membered heterocyclic rings.

Examples of nitrogen-containing heterocycles include L. G. Brooker et al., Journal of American Chemical Society, J. Am. Chem. Soc., Volume 73 (1951), p. Any of those known to constitute a basic nucleus in merocyanine dyes described in 5326-5358 and references can be suitably used.
Specific examples include thiazoles (for example, thiazole, 4-methylthiazole, 4-phenylthiazole, 5-methylthiazole, 5-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole, 4,5- Di (p-methoxyphenylthiazole), 4- (2-thienyl) thiazole, 4,5-di (2-furyl) thiazole, etc.), benzothiazoles (for example, benzothiazole, 4-chlorobenzothiazole, 5-chloro Benzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 4-phenylbenzothiazole, 5-phenylbenzothiazole 4-methoxybenzo Azole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-iodobenzothiazole, 6-iodobenzothiazole, 4-ethoxybenzothiazole, 5-ethoxybenzothiazole, tetrahydrobenzothiazole, 5,6-dimethoxybenzothiazole, 5,6-dioxymethylenebenzothiazole, 5-hydroxybenzothiazole, 6-hydroxybenzothiazole, 6-dimethylaminobenzothiazole, 5-ethoxycarbonylbenzothiazole, etc.), naphthothiazoles (for example, naphtho [1,2 ] Thiazole, naphtho [2,1] thiazole, 5-methoxynaphtho [2,1] thiazole, 5-ethoxynaphtho [2,1] thiazole, 8-methoxynaphtho [1,2] thiazole, 7-methoxynaphtho [ , 2] thiazole, etc.), thianaphtheno-7 ′, 6 ′, 4,5-thiazole (for example, 4′-methoxythianaphtheno-7 ′, 6 ′, 4,5-thiazole, etc.), oxazole ( For example, 4-methyl oxazole, 5-methyl oxazole, 4-phenyl oxazole, 4,5-diphenyl oxazole, 4-ethyl oxazole, 4,5-dimethyl oxazole, 5-phenyl oxazole, etc.), benzoxazoles (benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-phenylbenzoxazole, 6-methylbenzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, 6-methoxybenzoxazole, 5-methoxybenzo Oxazole, 4-ethoxy Nzooxazole, 5-chlorobenzoxazole, 6-methoxybenzoxazole, 5-hydroxybenzoxazole, 6-hydroxybenzoxazole, etc.), naphthoxazoles (for example, naphtho [1,2] oxazole, naphtho [2,1 Oxazole, etc.), selenazoles (eg, 4-methylselenazole, 4-phenylselenazole, etc.), benzoselenazoles (eg, benzoselenazole, 5-chlorobenzoselenazole, 5-methoxybenzoselenazole) , 5-hydroxybenzoselenazole, tetrahydrobenzoselenazole, etc.), naphthoselenazoles (for example, naphtho [1,2] selenazole, naphtho [2,1] selenazole, etc.), thiazolines (for example, thiazoline, 4 -Methylthiazoline 4,5-dimethylthiazoline, 4-phenylthiazoline, 4,5-di (2-furyl) thiazoline, 4,5-diphenylthiazoline, 4,5-di (p-methoxyphenyl) thiazoline, etc.), 2-quinolines (For example, quinoline, 3-methylquinoline, 5-methylquinoline, 7-methylquinoline, 8-methylquinoline, 6-chloroquinoline, 8-chloroquinoline, 6-methoxyquinoline, 6-ethoxyquinoline, 6-hydroxyquinoline, 8-hydroxyquinoline, etc.), 4-quinolines (eg, quinoline, 6-methoxyquinoline, 7-methylquinoline, 8-methylquinoline, etc.), 1-isoquinolines (eg, isoquinoline, 3,4-dihydroisoquinoline) Etc.), 3-isoquinolines (for example, isoquinoline etc.), benzimidazoles (Eg, 1,3-dimethylbenzimidazole, 1,3-diethylbenzimidazole, 1-ethyl-3-phenylbenzimidazole, etc.), 3,3-dialkylindolenins (eg, 3,3-dimethylindolenin) 3,3,5-trimethylindolenine, 3,3,7-trimethylindolenine, etc.), 2-pyridines (for example, pyridine, 5-methylpyridine, etc.), 4-pyridine (for example, pyridine, etc.) Etc. Moreover, the substituents of these rings may combine to form a ring.

Examples of the sulfur-containing heterocycle include a dithiol partial structure in dyes described in JP-A-3-296759.
Specific examples include benzodithiols (for example, benzodithiol, 5-t-butylbenzodithiol, 5-methylbenzodithiol, etc.), naphthodithiols (for example, naphtho [1,2] dithiol, naphtho [2,1 Dithiols, etc.), dithiols (for example, 4,5-dimethyldithiols, 4-phenyldithiols, 4-methoxycarbonyldithiols, 4,5-dimethoxycarbonyldithiols, 4,5-diethoxycarbonyldithiols) 4,5-ditrifluoromethyldithiol, 4,5-dicyanodithiol, 4-methoxycarbonylmethyldithiol, 4-carboxymethyldithiol, etc.).

Among the examples of the nitrogen-containing or sulfur-containing heterocyclic ring formed by Y ^{6 in} cooperation with the above-described A ⁶ and the adjacent carbon atom in the general formula (12) described above, the partial structure of the following general formula (13) The dye having the structure represented by the formula is particularly preferable because it gives a photosensitive composition having high sensitizing ability and very excellent storage stability.

In the general formula ^{(13), A 6, X} 15, R 56, R 57, R 58 has the same meaning as ^{A 6, X 15, R 56} , R 57, R 58 in formula (12). R ⁵⁹ is synonymous with R ⁵⁶ .

  The compound represented by the general formula (12) is more preferably a compound represented by the following general formula (14).

In the general formula ^{(14), A 6, X} 15, R 56, R 57, R 58 has the same meaning as ^{A 6, X 15, R 56} , R 57, R 58 in formula (12).
Ar represents an aromatic ring or a heterocyclic ring having a substituent. However, the substituents on the Ar skeleton need to have a sum of Hammett values greater than zero. Here, the sum of the Hammett values is greater than 0 means that the substituent has one substituent, and the Hammett value of the substituent may be greater than 0, and has a plurality of substituents. The sum of Hammett values at may be greater than zero.
Moreover, Ar represents an aromatic ring or a hetero ring having a substituent, specific examples, among those described in the description of A ⁶ in the previous general formula (12), an aromatic ring or a heterocyclic having substituent The specific example which concerns on a ring is mentioned similarly. However, as a substituent that can be introduced into Ar in the general formula (14), it is essential that the sum of Hammett values is 0 or more. Examples of such a substituent include a trifluoromethyl group and a carbonyl group. , Ester groups, halogen atoms, nitro groups, cyano groups, sulfoxide groups, amide groups, carboxyl groups and the like. The Hammett values of these substituents are shown below. Trifluoromethyl group (—CF ₃ , m: 0.43, p: 0.54), carbonyl group (eg, —COHm: 0.36, p: 0.43), ester group (—COOCH ₃ , m: 0 .37, p: 0.45), halogen atom (eg, Cl, m: 0.37, p: 0.23), cyano group (—CN, m: 0.56, p: 0.66), sulfoxide group (e.g. _{-SOCH 3, m: 0.52, p} : 0.45), amide groups (e.g. _{-NHCOCH 3, m: 0.21, p} : 0.00), carboxyl group (-COOH, m: 0. 37, p: 0.45). The parenthesis represents the introduction position of the substituent in the aryl skeleton and the Hammett value, and (m: 0.50) is the Hammett value of 0.50 when the substituent is introduced at the meta position. Indicates that there is. Among these, preferable examples of Ar include a phenyl group having a substituent, and preferable substituents on the Ar skeleton include an ester group and a cyano group. The substitution position is particularly preferably located at the ortho position on the Ar skeleton.

  Although the preferable specific example (D1-D57) of the sensitizing dye represented by General formula (12) below is shown, this invention is not limited to these. Among these, those corresponding to the compound represented by the general formula (13) are D2, D6, D10, D18, D21, D28, D31, D33, D35, D38, D41, and D45 to D57.

A method for synthesizing the compound represented by the general formula (12) will be described.
The compound represented by the general formula (12) is usually obtained by a condensation reaction between an acidic nucleus having an active methylene group and a substituted or unsubstituted aromatic ring or heterocyclic ring. These compounds are described in JP-B-59-28329. And can be synthesized. For example, as shown in the following reaction formula (1), a synthesis method using a condensation reaction of an acidic nucleus compound and a basic nucleus raw material having an aldehyde group or a carbonyl group on the heterocycle can be mentioned. The condensation reaction is carried out in the presence of a base as necessary. As the base, generally used ones such as amines, pyridines (trialkylamine, dimethylaminopyridine, diazabicycloundecene DBU, etc.), metal amides (lithium diisopropylamide, etc.), metal alkoxides ( Sodium methoxide, potassium-t-butoxide, etc.) and metal hydrides (sodium hydride, potassium hydride, etc.) can be used without limitation.

Another desirable synthesis method is a method according to the following reaction formula (2). That is, as an acidic nucleus compound in the reaction formula (1), an acidic nucleus compound in which Y ⁶ is a sulfur atom is used as a starting material, and a dye is formed by a condensation reaction of a basic nucleus material having an aldehyde group or a carbonyl group on a heterocycle. The process up to the step of synthesizing the precursor is carried out in the same manner as in the reaction formula (1), and then the dye precursor is further interacted with a sulfur atom to form a metal sulfide and water or a metal salt that can form a metal sulfide. This is a reaction in which a primary amine compound (R ⁶⁰ —NH _2, where R ⁶⁰ represents a monovalent nonmetallic atomic group) is allowed to act.
Among these, the reaction represented by the reaction formula (2) has a high yield of each reaction and is particularly preferable in terms of synthesis efficiency. In particular, this reaction is used when the compound represented by the general formula (13) is synthesized. The reaction represented by formula (2) is useful.

In the reaction formula (2), M ^{n +} X ¹⁶ _n represents a metal salt that can chemically interact with the sulfur atom of the thiocarbonyl group to form a metal sulfide. As specific compounds, for example, M is Al, Au, Ag, Hg, Cu, Zn, Fe, Cd, Cr, Co, Ce, Bi, Mn, Mo, Ga, Ni, Pd, Pt, Ru, Rh. , Sc, Sb, Sr, Mg, Ti, etc., and X is F, Cl, Br, I, NO ₃ , SO ₄ , NO ₂ , PO ₄ , CH ₃ CO _2, etc., AgBr, AgI, AgF, AgO, AgCl, Ag ₂ O, Ag (NO ₃ ), AgSO ₄ , AgNO ₂ , Ag ₂ CrO ₄ , Ag ₃ PO ₄ , Hg ₂ (NO ₃ ) ₂ , HgBr ₂ , Hg ₂ Br ₂ , HgO, HgI ₂ , Hg (NO ₃ ) ₂ , Hg (NO ₂ ) ₂ , HgBr ₂ , HgSO ₄ , Hg ₂ I ₂ , Hg ₂ SO ₄ , Hg (CH ₃ CO ₂ ) ₂ , AuBr, AuBr ₃ , AuI, AuI ₃ , AuF ₃ , Au ₂ O ₃ , AuCl, AuC 1 ₃ , CuCl, CuI, CuI ₂ , CuF ₂ , CuO, CuO ₂ , Cu (NO ₃ ) ₂ , CuSO ₄ , Cu ₃ (PO ₄ ) ₂ . Among these, a silver salt can be used as the most preferable metal salt in that it easily interacts with a sulfur atom.

The sensitizing dye represented by the general formula (12) used in the present invention can be further subjected to various chemical modifications for improving the characteristics of the photosensitive layer. For example, (D) a sensitizing dye and (B) an addition polymerizable compound structure (for example, acryloyl group or methacryloyl group) are bonded by a method such as covalent bond, ionic bond, hydrogen bond, etc. It is possible to increase the strength and to suppress unnecessary precipitation of the dye from the film after exposure.
In addition, partial structures having radical generating ability in the sensitizing dye and the aforementioned initiator compound (for example, reductive decomposable sites such as alkyl halides, oniums, peroxides, biimidazoles, borate, amine, trimethylsilylmethyl, carboxy The photosensitivity can be remarkably enhanced particularly in a state where the concentration of the starting system is low.

Further, when the photosensitive composition of the present invention is used as a photosensitive layer of a lithographic printing plate precursor which is a preferred mode of use, it is hydrophilic for the purpose of enhancing the suitability for processing in an alkaline or aqueous developer. It is effective to introduce a functional moiety (carboxyl group and its ester, sulfonic acid group and its ester, ethylene oxide group or other acid group or polar group). In particular, ester-type hydrophilic groups have a relatively hydrophobic structure in the photosensitive layer, so that they have excellent compatibility, and in the developer, acid groups are generated by hydrolysis, resulting in increased hydrophilicity. Have.
In addition, for example, a substituent can be appropriately introduced in order to improve compatibility in the photosensitive layer and to suppress crystal precipitation. For example, in certain types of photosensitive systems, unsaturated bonds such as aryl groups and allyl groups may be very effective in improving compatibility. By introducing the obstacle, crystal precipitation can be remarkably suppressed. Further, by introducing a phosphonic acid group, an epoxy group, a trialkoxysilyl group, or the like, adhesion to an inorganic substance such as a metal or a metal oxide can be improved. In addition, a method such as polymerization of a sensitizing dye can be used depending on the purpose.

As the sensitizing dye used in the present invention, it is preferable to use at least one sensitizing dye represented by the general formula (12). As long as the general formula (12) indicates, for example, the modification described above The details of the usage, such as what kind of structure is used, such as those that have been used, whether they are used alone or in combination of two or more, and how much is added, match the performance design of the final photosensitive material Can be set as appropriate. For example, the compatibility with the photosensitive layer can be increased by using two or more sensitizing dyes in combination.
In selecting the sensitizing dye, in addition to the photosensitivity, the molar extinction coefficient at the emission wavelength of the light source used is an important factor. By using a dye having a large molar extinction coefficient, the amount of the dye added can be made relatively small, which is economical and advantageous from the viewpoint of film properties of the photosensitive layer.
In the present invention, not only the sensitizing dye represented by the general formula (12) but also other general-purpose sensitizing dyes can be used as long as the effects of the present invention are not impaired.

Since the photosensitivity and resolution of the photosensitive layer and the physical properties of the exposure film are greatly affected by the absorbance at the light source wavelength, the addition amount of the sensitizing dye is appropriately selected in consideration of these. For example, the sensitivity decreases in a low region where the absorbance is 0.1 or less. Also, the resolution becomes low due to the influence of halation. However, for the purpose of curing a thick film of, for example, 5 μm or more, there is a case where such a low absorbance can be increased instead. Further, in a region where the absorbance is as high as 3 or more, most of the light is absorbed on the surface of the photosensitive layer, and the internal curing is inhibited. For example, when used as a printing plate, the film strength and the substrate adhesion are poor. It will be insufficient.
For example, when the photosensitive composition of the present invention is used in the photosensitive layer of a lithographic printing plate precursor using a relatively thin film thickness, the amount of the sensitizing dye added is such that the absorbance of the photosensitive layer is 0.1 to 1. It is preferable to set it in the range of .5, preferably in the range of 0.25 to 1. Since the absorbance is determined by the addition amount of the sensitizing dye and the thickness of the photosensitive layer, the predetermined absorbance can be obtained by controlling both conditions. The absorbance of the photosensitive layer can be measured by a conventional method. As a measuring method, for example, on a transparent or white support, a photosensitive layer having a thickness appropriately determined in a range where the coating amount after drying is necessary as a lithographic printing plate is formed, and a transmission type optical densitometer is used. Examples thereof include a method of measuring, a method of forming a photosensitive layer on a reflective support such as aluminum, and measuring a reflection density.

[(D ′) Infrared absorbing dye]
When exposure using a laser emitting infrared rays as a light source is performed, it is preferable to contain an infrared absorbing dye having a maximum absorption wavelength between 750 and 1,400 nm. The infrared absorbing dye has a function of converting absorbed infrared rays into heat. The heat generated at this time promotes thermal decomposition of the radical generator (polymerization initiator). The infrared absorbing dye used in the present invention is a dye or pigment having an absorption maximum at a wavelength of 750 to 1,400 nm.

As the dye, commercially available dyes and known dyes described in documents such as “Dye Handbook” (edited by the Society for Synthetic Organic Chemistry, published in 1970) can be used. Specifically, dyes such as azo dyes, metal complex azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, metal thiolate complexes, etc. Is mentioned.
Preferred dyes include, for example, cyanine dyes described in JP-A-58-125246, JP-A-59-84356, JP-A-59-202829, JP-A-60-78787, and the like. Methine dyes described in JP-A-58-173696, JP-A-58-181690, JP-A-58-194595, JP-A-58-112793, JP-A-58-224793, JP-A-59- 48187, JP-A-59-73996, JP-A-60-52940, JP-A-60-63744, etc., naphthoquinone dyes, JP-A-58-112792, etc. And cyanine dyes described in British Patent 434,875.

Also, a near infrared absorption sensitizer described in US Pat. No. 5,156,938 is preferably used, and a substituted arylbenzo (thio) pyrylium salt described in US Pat. No. 3,881,924, Trimethine thiapyrylium salts described in JP-A-57-142645 (US Pat. No. 4,327,169), JP-A-58-181051, 58-220143, 59-41363, 59-84248 Nos. 59-84249, 59-146063, 59-146061, pyranlium compounds, cyanine dyes described in JP-A-59-216146, U.S. Pat. No. 4,283,475 The pentamethine thiopyrylium salts described above and the pyrylium compounds disclosed in Japanese Patent Publication Nos. 5-13514 and 5-19702 are also preferably used. . Moreover, as another example preferable as a dye, the near-infrared absorptive dye described as Formula (I) and (II) in US Patent 4,756,993 can be mentioned.
Other preferable examples of the infrared absorbing dye in the invention include specific indolenine cyanine dyes described in Japanese Patent Application Nos. 2001-6326 and 2001-237840 as exemplified below.

  Particularly preferred among these dyes are cyanine dyes, squarylium dyes, pyrylium salts, nickel thiolate complexes, and indolenine cyanine dyes. Further, cyanine dyes and indolenine cyanine dyes are preferable, and particularly preferable examples include infrared absorbers represented by the following general formulas (a) to (e).

In the general formula (a), X ¹⁷ represents a hydrogen atom, a halogen atom, —NPh ₂ , —X ¹⁶ -L ¹ or a group shown below. Here, X ¹⁶ represents an oxygen atom, a nitrogen atom, or a sulfur atom, and L ¹ represents a hydrocarbon group having 1 to 12 carbon atoms, an aromatic ring having a hetero atom, or 1 to 1 carbon atom containing a hetero atom. 12 hydrocarbon groups are shown. In addition, a hetero atom here shows N, S, O, a halogen atom, and Se. Xa ^- the Za described later ^- is defined as for, R ^a represents a hydrogen atom, an alkyl group, an aryl group, a substituted or unsubstituted amino group, substituted or unsubstituted amino group and a halogen atom.

R ⁶¹ and R ⁶² each independently represent a hydrocarbon group having 1 to 12 carbon atoms. In view of storage stability of the photosensitive layer coating solution, R ⁶¹ and R ⁶² are preferably hydrocarbon groups having 2 or more carbon atoms, and R ⁶¹ and R ⁶² are bonded to each other to form a 5-membered ring or It is particularly preferable that a 6-membered ring is formed.

Ar ¹ and Ar ² may be the same or different and each represents an aromatic hydrocarbon group which may have a substituent. Preferred aromatic hydrocarbon groups include a benzene ring and a naphthalene ring. Moreover, as a preferable substituent, a C12 or less hydrocarbon group, a halogen atom, and a C12 or less alkoxy group are mentioned. Y ⁷ and Y ⁸ may be the same or different and each represents a sulfur atom or a dialkylmethylene group having 12 or less carbon atoms. R ⁶³ and R ⁶⁴ may be the same or different and each represents a hydrocarbon group having 20 or less carbon atoms which may have a substituent. Preferred substituents include alkoxy groups having 12 or less carbon atoms, carboxyl groups, and sulfo groups. R ⁶⁵ , R ⁶⁶ , R ⁶⁷ and R ⁶⁸ may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 12 or less carbon atoms. From the availability of raw materials, a hydrogen atom is preferred. Za ⁻ represents a counter anion. However, Za ⁻ is not necessary when the cyanine dye represented by formula (a) has an anionic substituent in its structure and neutralization of charge is not necessary. Preferred Za ⁻ is a halogen ion, a perchlorate ion, a tetrafluoroborate ion, a hexafluorophosphate ion, and a sulfonate ion, particularly preferably a perchlorate ion, a hexagonal salt, in view of the storage stability of the photosensitive layer coating solution. Fluorophosphate ions and aryl sulfonate ions.

  Specific examples of the cyanine dye represented by formula (a) that can be suitably used in the present invention include those exemplified below, and paragraph numbers [0017] to [0017] of Japanese Patent Application No. 11-310623. [0019], paragraphs [0012] to [0038] of Japanese Patent Application No. 2000-224031, and paragraphs [0012] to [0023] of Japanese Patent Application No. 2000-2111147. .

In the general formula (b), L represents a methine chain having 7 or more conjugated carbon atoms, the methine chain may have a substituent, and the substituents may be bonded to each other to form a ring structure. Good. Z _b ⁺ represents a counter cation. Preferred counter cations include ammonium, iodonium, sulfonium, phosphonium, pyridinium, alkali metal cations (Na ⁺ , K ⁺ , Li ⁺ ) and the like. R ^{69 to} R ⁷⁴ and R ^{75 to} R ⁸⁰ are each independently a hydrogen atom or halogen atom, cyano group, alkyl group, aryl group, alkenyl group, alkynyl group, carbonyl group, thio group, sulfonyl group, sulfinyl group, oxy group Or a substituent selected from amino groups, or a combination of two or three of these, and may be bonded to each other to form a ring structure. Here, in general formula (b), L represents a methine chain having 7 conjugated carbon atoms, and R ^{69 to} R ⁷⁴ and R ^{75 to} R ⁸⁰ all represent hydrogen atoms are easily available. It is preferable from the viewpoint of effect.

  Specific examples of the dye represented by formula (b) that can be suitably used in the present invention include those exemplified below.

In the general formula (c), Y ⁹ and Y ¹⁰ each represent an oxygen atom, a sulfur atom, a selenium atom, or a tellurium atom. M represents a methine chain having 5 or more conjugated carbon atoms. R ^{81 to} R ⁸⁴ and R ^{85 to} R ⁸⁸ may be the same or different, and are each a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a carbonyl group, thio Represents a group, a sulfonyl group, a sulfinyl group, an oxy group, or an amino group. Further, wherein Za ^- include a counter anion, Za in the general formula (a) ^- it is synonymous.

  In the present invention, specific examples of the dye represented by formula (c) that can be suitably used include those exemplified below.

In the general formula (d), R ⁸⁹ to R ⁹¹ each independently represent a hydrogen atom, an alkyl group, or an aryl group.
R ⁹³ and R ⁹⁴ each independently represents an alkyl group, a substituted oxy group, or a halogen atom.
n and m each independently represents an integer of 0 to 4.
R ⁸⁹ and R ⁹⁰ , or R ⁹¹ and R ⁹² may be bonded to each other to form a ring, and R ⁸⁹ and / or R ⁹⁰ are R ⁹³ and R ⁹¹ and / or R ⁹² are R ⁹⁴ and They may be bonded to form a ring, and when there are a plurality of R ⁹³ or R ⁹⁴ , R ⁹³ or R ⁹⁴ may be bonded to each other to form a ring.
X ¹⁸ and X ¹⁹ each independently represent a hydrogen atom, an alkyl group, or an aryl group, and at least one of X ¹⁸ and X ¹⁹ represents a hydrogen atom or an alkyl group.
Q ³ is a trimethine group or a pentamethine group which may have a substituent, and may form a ring structure together with a divalent organic group. Zc ^- represents a counter anion, Za in the general formula (a) ^- synonymous.

  In the present invention, specific examples of the dye represented by the general formula (d) that can be suitably used include those exemplified below.

In the general formula (e), R ^{95 to} R ¹¹⁰ are each independently a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a hydroxyl group, a carbonyl group, a thio group, a sulfonyl group, or a sulfinyl group. When a group, an oxy group, an amino group, or an onium salt structure is shown and a substituent can be introduced into these groups, it may have a substituent. M represents two hydrogen atoms or metal atoms, a halometal group, and an oxymetal group, and the metal atoms contained therein include IA, IIA, IIIB, IVB group atoms of the periodic table, first, second, second Three-period transition metals and lanthanoid elements can be mentioned, among which copper, magnesium, iron, zinc, cobalt, aluminum, titanium, and vanadium are preferable.

  In the present invention, specific examples of the dye represented by formula (e) that can be suitably used include those exemplified below.

  Examples of the pigment used in the present invention include commercially available pigments and color index (CI) manual, “Latest Pigment Handbook” (edited by Japan Pigment Technology Association, published in 1977), “Latest Pigment Application Technology” (CMC Publishing, 1986), “Printing Ink Technology”, CMC Publishing, 1984) can be used.

  Examples of the pigment include black pigments, yellow pigments, orange pigments, brown pigments, red pigments, purple pigments, blue pigments, green pigments, fluorescent pigments, metal powder pigments, and other polymer-bonded dyes. Specifically, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelate azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments In addition, quinophthalone pigments, dyed lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, carbon black, and the like can be used. Among these pigments, carbon black is preferable.

  These pigments may be used without surface treatment, or may be used after surface treatment. The surface treatment method includes a method of surface coating with a resin or wax, a method of attaching a surfactant, a method of bonding a reactive substance (eg, silane coupling agent, epoxy compound, polyisocyanate, etc.) to the pigment surface, etc. Can be considered. The above-mentioned surface treatment methods are described in “Characteristics and Applications of Metal Soap” (Shobobo), “Printing Ink Technology” (CMC Publishing, 1984) and “Latest Pigment Application Technology” (CMC Publishing, 1986). Yes.

  The particle diameter of the pigment is preferably in the range of 0.01 μm to 10 μm, more preferably in the range of 0.05 μm to 1 μm, and particularly preferably in the range of 0.1 μm to 1 μm. When the particle diameter of the pigment is 0.01 μm or more, the stability of the dispersion in the image-sensitive layer coating solution is increased, and when it is 10 μm or less, the uniformity of the image-sensitive layer is improved.

  As a method for dispersing the pigment, a known dispersion technique used in ink production, toner production, or the like can be used. Examples of the disperser include an ultrasonic disperser, a sand mill, an attritor, a pearl mill, a super mill, a ball mill, an impeller, a disperser, a KD mill, a colloid mill, a dynatron, a three-roll mill, and a pressure kneader. Details are described in "Latest Pigment Applied Technology" (CMC Publishing, 1986).

The (D) sensitizing dye and (D ′) infrared absorbing dye added to accelerate the curing of the component (B) are the photosensitive layer of the negative planographic printing plate precursor as the component (B) in the present invention. May be added to the photosensitive layer, or another layer such as the undercoat layer may be provided and added thereto. In particular, when the component (B) in the present invention is applied to the photosensitive layer of a negative photosensitive lithographic printing plate, from the viewpoint of the sensitivity of the photosensitive layer, (D) when a sensitizing dye is used in the photosensitive layer. The optical density at the absorption maximum in the wavelength range of 350 nm to 450 nm of the photosensitive layer is preferably between 0.1 and 3.0, and (D ′) when an infrared absorbing dye is used for the photosensitive layer The optical density at the absorption maximum in the wavelength range of 750 nm to 1400 nm of the photosensitive layer is preferably between 0.1 and 3.0. Since the optical density is determined by the amount of the infrared absorbing dye added and the thickness of the photosensitive layer, the predetermined optical density can be obtained by controlling both conditions.
The optical density of the photosensitive layer can be measured by a conventional method. As a measuring method, for example, on a transparent or white support, a photosensitive layer having a thickness appropriately determined in a range where the coating amount after drying is necessary as a lithographic printing plate is formed, and a transmission type optical densitometer is used. Examples thereof include a method of measuring, a method of forming a photosensitive layer on a reflective support such as aluminum, and measuring a reflection density.

  When the photosensitive composition of the present invention is used as a photosensitive layer of a lithographic printing plate precursor, the amount of (D) sensitizing dye added is usually 0 with respect to 100 parts by mass of the total solid component constituting the photosensitive layer. 0.05 to 30 parts by mass, preferably 0.1 to 20 parts by mass, and more preferably 0.2 to 10 parts by mass.

[(F) Other ingredients]
In addition to the above components, the polymerizable composition in the present invention, for example, a co-sensitizer, a polymerization inhibitor, a colorant, a plasticizer, and other components suitable for its use and production method are appropriately added. can do. Hereinafter, preferred additives when the polymerizable composition of the invention is applied as a photosensitive layer of a negative type image recording material will be exemplified.

(Co-sensitizer)
By using a co-sensitizer for the photopolymerizable photosensitive layer, the sensitivity of the photosensitive layer can be further improved. These mechanisms of action are not clear, but many are thought to be based on the following chemical processes. That is, various intermediate active species (radicals, peroxides, oxidizing agents, reducing agents, etc.) generated in the course of the photoreaction initiated by light absorption of the above-mentioned photopolymerization initiator (system) and the subsequent addition polymerization reaction. It is presumed that the co-sensitizer reacts to generate a new active radical. These are broadly divided into (a) those capable of generating active radicals upon reduction, (b) those capable of being oxidized to generate active radicals, and (c) radicals having higher activity by reacting with radicals having lower activity. However, there are many cases where there is no general rule as to which individual compounds belong to them.

(A) Compound that is reduced to produce an active radical Compound having a carbon-halogen bond: It is considered that an active radical is generated by reductive cleavage of the carbon-halogen bond. Specifically, for example, trihalomethyl-s-triazines and trihalomethyloxadiazoles can be preferably used.

  Compound having nitrogen-nitrogen bond: It is considered that the nitrogen-nitrogen bond is reductively cleaved to generate an active radical. Specifically, hexaarylbiimidazoles and the like are preferably used.

  Compound having oxygen-oxygen bond: It is considered that the oxygen-oxygen bond is reductively cleaved to generate an active radical. Specifically, for example, organic peroxides are preferably used.

Onium compounds: It is considered that carbon-hetero bonds and oxygen-nitrogen bonds are reductively cleaved to generate active radicals. Specifically, for example, diaryliodonium salts, triarylsulfonium salts, N-alkoxypyridinium (azinium) salts and the like are preferably used.
Ferrocene and iron arene complexes: An active radical can be reductively generated.

(B) Compound which is oxidized to generate an active radical Alkylate complex: It is considered that a carbon-hetero bond is oxidatively cleaved to generate an active radical. Specifically, for example, triarylalkyl borates are preferably used.

  Alkylamine compound: It is considered that the C—X bond on carbon adjacent to nitrogen is cleaved by oxidation to generate an active radical. X is preferably a hydrogen atom, a carboxyl group, a trimethylsilyl group, a benzyl group or the like. Specific examples include ethanolamines, N-phenylglycines, N-trimethylsilylmethylanilines, and the like.

  Sulfur-containing and tin-containing compounds: Compounds in which the nitrogen atoms of the above-described amines are replaced with sulfur atoms and tin atoms can generate active radicals by the same action. Further, a compound having an SS bond is also known to be sensitized by SS cleavage.

  α-Substituted methylcarbonyl compound: An active radical can be generated by oxidative cleavage of the carbonyl-α carbon bond. Moreover, what converted carbonyl into the oxime ether also shows the same effect | action. Specifically, 2-alkyl-1- [4- (alkylthio) phenyl] -2-morpholinopronone-1 and oximes obtained by reacting these with hydroxyamines and then etherifying N—OH Mention may be made of ethers.

  Sulfinic acid salts: An active radical can be reductively generated. Specific examples include sodium arylsulfinate.

(C) Compounds that react with radicals to convert into highly active radicals or act as chain transfer agents For example, a group of compounds having SH, PH, SiH, GeH in the molecule is used. These can generate hydrogen by donating hydrogen to a low-activity radical species to generate radicals, or after being oxidized and deprotonated. Specifically, 2-mercaptobenzimidazoles etc. are mentioned, for example.

  More specific examples of these co-sensitizers are described, for example, in JP-A-9-236913 as additives for the purpose of improving sensitivity. Some examples are shown below, but those used for the photosensitive layer of the lithographic printing plate precursor according to the invention are not limited thereto.

These cosensitizers can also be subjected to various chemical modifications for improving the characteristics of the photosensitive layer. For example, bonds with sensitizing dyes, titanocene, addition polymerizable unsaturated compounds and other radical generating parts, introduction of hydrophilic sites, improved compatibility, introduction of substituents for suppressing crystal precipitation, substituents for improving adhesion Methods such as introduction and polymerization can be used.

  These co-sensitizers can be used alone or in combination of two or more. The amount used is 0.05 to 100 parts by mass, preferably 1 to 80 parts by mass, and more preferably 3 to 50 parts by mass with respect to 100 parts by mass of the compound having an ethylenically unsaturated double bond.

(Polymerization inhibitor)
In addition, in the photo- or heat-polymerizable negative photosensitive layer of a lithographic printing plate precursor to which the polymerizable composition according to the present invention is applied, an ethylenic polymer that can be polymerized during the production or storage of the negative photosensitive composition. In order to prevent unnecessary thermal polymerization of the compound having a saturated double bond, it is desirable to add a small amount of a thermal polymerization inhibitor. Suitable thermal polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol ), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like. The addition amount of the thermal polymerization inhibitor is preferably about 0.01% by mass to about 5% by mass with respect to the mass of the nonvolatile components in the entire composition. If necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to prevent polymerization inhibition due to oxygen, and it may be unevenly distributed on the surface of the photosensitive layer in the course of drying after coating. . The addition amount of the higher fatty acid derivative is preferably about 0.5% by mass to about 10% by mass with respect to the nonvolatile components in the entire composition.

(Coloring agent)
Furthermore, when the polymerizable composition in the present invention is applied to the photosensitive layer of a lithographic printing plate precursor, a dye or pigment may be added for the purpose of coloring. Thereby, so-called plate inspection properties such as visibility after plate making and suitability for an image density measuring machine as a printing plate can be improved. As the colorant, many dyes cause a decrease in the sensitivity of the photopolymerization type photosensitive layer. Therefore, it is particularly preferable to use a pigment as the colorant. Specific examples include pigments such as phthalocyanine pigments, azo pigments, carbon black and titanium oxide, and dyes such as ethyl violet, crystal violet, azo dyes, anthraquinone dyes, and cyanine dyes. The addition amount of the dye and the pigment is preferably about 0.5% by mass to about 5% by mass with respect to the nonvolatile components in the entire composition.

(Other additives)
Furthermore, in order to improve the physical properties of the cured film, inorganic fillers, other plasticizers, and ink deposition on the surface of the photosensitive layer when the polymerizable composition of the present invention is applied to the photosensitive layer of a lithographic printing plate precursor You may add well-known additives, such as a fat-sensitizing agent which can improve property.

  Examples of plasticizers include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin, etc., polymer binder and addition polymerizable compound In general, it can be added in a range of 10% by mass or less with respect to the total mass.

  Further, for the purpose of improving the film strength (printing durability), which will be described later, a UV initiator, a thermal crosslinking agent, or the like can be added to enhance the effect of heating and exposure after development.

(solvent)
The photosensitive layer in the present invention is formed by dissolving the constituent components of the photosensitive layer in various organic solvents and coating the coating solution on the above-described undercoat layer.
Solvents used here include acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, Acetylacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, methyl lactate, lactic acid There are ethyl and the like. These solvents can be used alone or in combination. The solid content in the coating solution is suitably 2 to 50% by mass.

The coating amount of the photosensitive layer mainly affects the sensitivity of the photosensitive layer, the developability, the strength of the exposed film, and the printing durability, and is preferably selected as appropriate according to the application. If the coating amount is too small, the printing durability is not sufficient. On the other hand, when the amount is too large, the sensitivity is lowered, it takes time for exposure, and a longer time is required for development processing, which is not preferable. As the lithographic printing plate precursor for scanning exposure which is the main object of the present invention, the coating amount is suitably in the range of 0.1 to 10 g / m ² after drying. More preferably from 0.5 to 5 g / ^{m 2.}

[Intermediate layer, protective layer]
The lithographic printing plate precursor according to the invention may include other layers such as an intermediate layer (undercoat layer) and a protective layer, if necessary, in addition to the photosensitive layer.

(Middle layer)
The lithographic printing plate precursor according to the invention may be provided with an intermediate layer (hereinafter referred to as “undercoat layer” as appropriate) for the purpose of improving the adhesion and stain resistance between the undercoat layer and the photosensitive layer. . Specific examples of such an intermediate layer include JP-B-50-7481, JP-A-51-71123, JP-A-54-72104, JP-A-59-101651, JP-A-60. -14991, JP-A-60-232998, JP-A-2-304441, JP-A-3-56177, JP-A-4-282737, JP-A-5-16558, JP-A-5- No. 246171, JP-A-5-341532, JP-A-7-159983, JP-A-7-314937, JP-A-8-202025, JP-A-8-320551, JP-A-9-34104 JP-A-9-236911, JP-A-9-269593, JP-A-10-69092, JP-A-10-115931, JP-A-10-161317, JP-A-10-260536, JP-A-10-282679, JP-A-10-282682, JP-A-11-84684, JP-A-10-69092, JP-A-10 -115931, JP-A-11-38635, JP-A-11-38629, JP-A-10-282645, JP-A-10-301262, JP-A-11-24277, JP-A-11-109641 JP-A-10-319600, JP-A-11-84684, JP-A-11-327152, JP-A-2000-10292, JP-A-11-36377, JP-A-11- No. 165861, Japanese Patent Application Laid-Open No. 2001-175001, Japanese Patent Application No. 2000-14697, etc. Mention may be made of.

(Protective layer)
As in the present invention, a lithographic printing plate precursor having a light- or heat-polymerizable negative photosensitive layer usually has a protective layer on the photosensitive layer in order to perform exposure in the air. The protective layer prevents exposure of low molecular weight compounds such as oxygen and basic substances present in the atmosphere that hinder the image formation reaction caused by exposure in the photosensitive layer, and enables exposure in the atmosphere. To do. Therefore, the properties desired for such a protective layer are low permeability of low-molecular compounds such as oxygen, and further, transmission of light used for exposure is not substantially inhibited, and adhesion to the photosensitive layer is excellent. And it is desirable that it can be easily removed in the development process after exposure. The device concerning such a protective layer has been conventionally made, and is described in detail in US Pat. No. 3,458,311 and JP-B-55-49729.

As a material that can be used for the protective layer, for example, a water-soluble polymer compound having relatively excellent crystallinity is preferably used. Specifically, polyvinyl alcohol, polyvinyl pyrrolidone, acidic celluloses, gelatin, gum arabic, Water-soluble polymers such as acrylic acid are known, but among these, using polyvinyl alcohol as a main component gives the best results in terms of basic properties such as oxygen barrier properties and development removability. The polyvinyl alcohol used for the protective layer may be partially substituted with an ester, an ether and an acetal as long as it contains an unsubstituted vinyl alcohol unit for having necessary oxygen barrier properties and water solubility. Similarly, some of them may have other copolymer components. Specific examples of polyvinyl alcohol include those having a hydrolysis rate of 71 to 100% and a molecular weight in the range of 300 to 2400.
Specifically, Kuraray Co., Ltd. PVA-105, PVA-110, PVA-117, PVA-117H, PVA-120, PVA-124, PVA-124H, PVA-CS, PVA-CST, PVA-HC, PVA-203, PVA-204, PVA-205, PVA-210, PVA-217, PVA-220, PVA-224, PVA-217EE, PVA-217E, PVA-220E, PVA-224E, PVA-405, PVA- 420, PVA-613, L-8 and the like.

  Examples of the copolymer include 88-100% hydrolyzed polyvinyl acetate chloroacetate or propionate, polyvinyl formal and polyvinyl acetal, and copolymers thereof. Other useful polymers include polyvinyl pyrrolidone, gelatin and gum arabic, and these may be used alone or in combination.

Examples of the polyvinyl alcohol suitably used in the present embodiment include those having a hydrolysis rate of 71 to 100% and a molecular weight in the range of 200 to 2400. It is more preferable to use polyvinyl alcohol having a saponification degree of 91 mol% or more from the viewpoint of high oxygen barrier properties, excellent film-forming properties, and a low adhesion surface.
Specifically, PVA-102, PVA-103, PVA-104, PVA-105, PVA-110, PVA-117, PVA-120, PVA-124, PVA-117H, PVA-135H made by Kuraray Co., Ltd. , PVA-HC, PVA-617, PVA-624, PVA-706, PVA-613, PVA-CS, PVA-CST, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., Gohsenol NL-05, NM-11, NM-14 , AL-06, P-610, C-500, A-300, AH-17, JF-04, JF-05, JF-10, JF-17, JF-17L, manufactured by Nihon Venture Bipoval Co., Ltd. , JM-05, JM-10, JM-17, JM-17L, JT-05, JT-13, JT-15 and the like.

Furthermore, what acid-modified polyvinyl alcohol is also used suitably. Specifically, itaconic acid and maleic acid modified carboxy modified polyvinyl alcohol and sulfonic acid modified polyvinyl alcohol are preferred. These acid-modified polyvinyl alcohols can also be used more preferably if the saponification degree is 91 mol% or more.
Specific examples of the acid-modified polyvinyl alcohol include KL-118, KM-618, KM-118, SK-5102, MP-102, R-2105, manufactured by Kuraray Co., Ltd., and Nippon Synthetic Chemical Industry Co., Ltd. , GOHSENAL CKS-50, T-HS-1, T-215, T-350, T-330, T-330H, AF-17, AT-17, etc. manufactured by Nihon Vinegar Poval Co., Ltd., and the like.

The above water-soluble polymer compound is 45 to 95% by mass with respect to the total solid content in the protective layer, considering the sensitivity of the obtained negative lithographic printing plate precursor and the adhesion between laminated lithographic printing plate precursors. It is preferable to contain in the range of 50-90 mass%, and it is more preferable to contain.
As the water-soluble polymer compound, at least one kind may be used, and a plurality of kinds may be used in combination. Even when a plurality of types of water-soluble polymer compounds are used in combination, the total amount is preferably in the above-described mass range.

The coating amount of the protective layer is 0.1 to 4.0 g from the viewpoint of maintaining the film strength and scratch resistance of the obtained oxygen blocking layer, maintaining the image quality, and maintaining appropriate oxygen permeability for imparting safelight suitability. / M ² is preferable, and 0.3 to 3.0 g / m ² is more preferable.
Components of the protective layer (selection of PVA, use of additives), coating amount, and the like are selected in consideration of fogging, adhesion, and scratch resistance in addition to oxygen barrier properties and development removability. In general, the higher the hydrolysis rate of the PVA used (the higher the content of the unsubstituted vinyl alcohol unit in the protective layer), the higher the film thickness, the higher the oxygen barrier property and the more advantageous in terms of sensitivity. However, when the oxygen barrier property is extremely increased, problems such as unnecessary polymerization reaction during production and raw storage, and unnecessary fogging and image line weighting during image exposure occur. In addition, adhesion to the image area and scratch resistance are extremely important in handling the plate. That is, when a hydrophilic layer made of a water-soluble polymer is laminated on an oleophilic photosensitive layer, film peeling due to insufficient adhesion tends to occur, and the peeled part causes defects such as poor film hardening due to inhibition of oxygen polymerization. On the other hand, various proposals have been made to improve the adhesion between these two layers. For example, U.S. Patent Application No. 292,501 and U.S. Patent Application No. 44,563 disclose an acrylic emulsion or a water-insoluble vinylpyrrolidone-vinyl acetate copolymer in a hydrophilic polymer mainly composed of polyvinyl alcohol. It is described that sufficient adhesiveness can be obtained by mixing 20 to 60% by mass and the like and laminating on the photosensitive layer.
Any of these known techniques can be applied to the protective layer in the present invention. Such a coating method of the protective layer is described in detail, for example, in US Pat. No. 3,458,311 and JP-B-55-49729.
Furthermore, you may add various additives to this protective layer suitably. The preferred additives are specifically described below.

(Filler)
The protective layer in the present invention preferably has a filler. The filler of the protective layer has a function of matting the surface of the protective layer (function of imparting unevenness and reducing the surface area of the adhesive), preventing adhesion of the back surface of the protective layer, and preventing the protective layer surface from being scratched. Have.

  The filler used in the present invention suppresses adhesion between the protective layer surface of the lithographic printing plate precursor and the back surface of the adjacent lithographic printing plate precursor and scratches generated between the protective layer surface and the back surface of the aluminum support. It is added for this purpose. It is preferable that the basic characteristics desired for such a filler do not substantially impede the transmission of light used for exposure, are not softened by moisture in the air, or at a temperature of at least 60 ° C., and are not sticky. Further, a matting effect on the surface of the protective layer (an effect of imparting unevenness and reducing the adhesive surface area) is necessary, and as an index of surface unevenness, Bekk smoothness is 500 seconds or less, more preferably 150 seconds or less.

  As the filler, from the viewpoint of suppressing scratches, organic particles that are relatively soft, elastic, and capable of relieving stress generated when rubbed with a hard aluminum back surface are preferable. Organic resin fine particles are preferred. Among them, particles that are crosslinked so as not to be fused by heat are preferable. The fine particles preferably have a high affinity with the binder of the protective layer, are well kneaded in the film, and do not desorb from the film surface.

  Organic resins having such characteristics include poly (meth) acrylates, polystyrene and derivatives thereof, polyamides, polyimides, polyolefins such as low density polyethylene, high density polyethylene, polypropylene, and the like. Examples thereof include copolymers with POVAL, synthetic resin particles such as polyurethane, polyurea, and polyesters, and natural polymer particles such as chitin, chitosan, cellulose, and crosslinked starch and crosslinked cellulose. Among these, the synthetic resin particles have advantages such as easy particle size control and easy control of desired surface characteristics by surface modification. In such a method for producing fine particles of organic resin, a relatively hard resin can be finely divided by a crushing method, but a method of synthesizing particles by a suspension polymerization method is easy to control the particle size, Currently adopted in the mainstream due to its accuracy. The method for producing these fine particle powders is described in “Preparation and Application of Fine Particles / Powder”, published by Haruma Kawaguchi, published by CMC Publishing 2005 first edition. Commercially available products of these organic resin fine particles include cross-linked acrylic resins (MX-300, MX-500, MX-1000, MX-1500H, MR-2HG, MR-7HG, MR-10HG, MR-, manufactured by Soken Chemical Co., Ltd.). 3GSN, MR-5GSN, MR-7G, MR-10G, MR-5C, MR-7GC), manufactured by Soken Chemical Co., Ltd., styryl resin-based SX-350H, SX-500H, manufactured by Sekisui Plastics, acrylic resin ( (MBX-5, MBX-8, MBX-12MBX-15, MBX-20, MB20X-5, MB30X-5, MB30X-8, MB30X-20, SBX-6, SBX-8, SBX-12, SBX-17) Made by Mitsui Chemicals, polyolefin resin (Chemical Pearl W100, W200, W300, W308, W310, W400, W401, W4 5, W410, W500, WF640, W700, W800, W900, W950, WP100), and the like, such as.

  Moreover, you may mix and use 2 or more types of fillers, such as an inorganic filler and an inorganic-organic composite filler.

Examples of the inorganic filler include metals and metal compounds such as oxides, composite oxides, hydroxides, carbonates, sulfates, silicates, phosphates, nitrides, carbides, sulfides, and at least two of these. Specific examples of the composites include glass, zinc oxide, alumina, zircon oxide, tin oxide, potassium titanate, strontium titanate, aluminum borate, magnesium oxide, magnesium borate, aluminum hydroxide, and hydroxide. Magnesium, calcium hydroxide, titanium hydroxide, basic magnesium sulfate, calcium carbonate, magnesium carbonate, calcium sulfate, magnesium sulfate, calcium silicate, magnesium silicate, calcium phosphate, silicon nitride, titanium nitride, aluminum nitride, silicon carbide, carbonized A composite of titanium, zinc sulfide and at least two of these. Product, and the like. Preferred examples include glass, alumina, potassium titanate, strontium titanate, aluminum borate, magnesium oxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium phosphate, and calcium sulfate.
Specifically, Mizukasil P-510, P-526, P-603, P-604, P-527, P-802, P-553A, P-73, P-78A, P-78F, P made by Mizusawa Chemical Examples thereof include silica fine particles such as -705 and P-707.

Examples of the inorganic-organic composite filler include composites of the above organic filler and inorganic filler. Examples of the inorganic filler include metal powders, metal compounds (for example, oxides, nitrides, sulfides, carbides, and the like). Composite particles, etc., preferably oxides and sulfides, more preferably glass, SiO ₂ , ZnO, Fe ₂ O ₃ , ZrO ₂ , SnO ₂ , ZnS, CuS, and the like. It is done.

  Examples of the shape of the filler include a fibrous shape, a needle shape, a plate shape, a spherical shape, a granular shape (indefinite shape, hereinafter the same meaning), a tetrapot shape, a balloon shape, and the like. Of these, preferred are spherical and granular.

  The grain size distribution may be monodisperse or polydisperse emulsion, but monodispersion is preferred. The filler preferably has an average particle size of 1 to 20 μm, more preferably an average particle size of 2 to 15 μm, and still more preferably an average particle size of 3 to 10 μm. By setting it within these ranges, the effect of the present invention is more effectively expressed.

  The content of the filler is preferably 0.1 to 20% by mass, more preferably 1 to 15% by mass, and further preferably 2 to 10% by mass with respect to the total solid content of the protective layer.

Those fine particles, which are supplied in powder form, are dispersed in an aqueous solution of polyvinyl alcohol in the protective layer by a simple disperser such as a homogenizer, a homomixer, a ball mill, or a paint shaker. At this time, if necessary, a surfactant is added and dispersed to further stabilize the dispersed particles. As the surfactant used for such dispersion, any of a nonionic surfactant, an anionic surfactant, and a cationic surfactant can be used. Examples of nonionic surfactants include polyethylene glycol alkyl ethers, alkenyl ethers, polyethylene glycol alkyl esters, polyethylene glycol aryl ethers, and the like. Anionic surfactants include alkyl or aryl sulfonate type, alkyl or aryl sulfate ester type, alkyl or aryl phosphate ester type, alkyl or aryl carboxylate type surfactants. Examples of the cationic surfactant include alkylamine salt type, alkylpyridinium salt type, and alkylammonium salt type surfactants. More specifically, more specific examples of these surfactants are described in “Latest Surfactant Functional Creation / Material Development / Applied Technology” Teruo Horiuchi, edited by Toshiyuki Suzuki Can be mentioned.
Since the Mitsui Chemicals Chemie Pal series fine particles are supplied in a state of being dispersed in water, these dispersions are directly added to the protective layer aqueous solution and stirred to prepare a coating solution.

(Inorganic layered compound)
By containing an inorganic stratiform compound in the protective layer, the oxygen barrier property is further increased, and the hardness of the protective layer is also increased. As a result, in addition to the oxygen barrier property, the protective layer can also suppress deterioration due to deformation or the like and generation of scratches.

-Mica compound-
Examples of the inorganic layered compound include mica compounds such as natural mica and synthetic mica as represented by the following general formula.
General formula: A (B, C) _2-5 D ₄ O ₁₀ (OH, F, O) ₂
[However, A is any of K, Na, and Ca, B and C are any of Fe (II), Fe (III), Mn, Al, Mg, V, and D is Si or Al. is there. ]

Specific examples of mica represented by the above general formula and other examples used in the present invention include muscovite, soda mica, phlogopite, biotite, and micaceous mica. In addition, examples of the synthetic mica include non-swelling mica such as fluorine phlogopite mica KMg ₃ (AlSi ₃ O ₁₀ ) F ₂ and potash tetrasilicon mica KMg _2.5 (Si ₄ O ₁₀ ) F ₂ , and Na tetrasilic mica. NaMg _2.5 (Si ₄ O ₁₀ ) F ₂ , Na or Li Teniolite (Na, Li) Mg ₂ Li (Si ₄ O ₁₀ ) F ₂ , Montmorillonite Na or Li Hectorite (Na, Li) _1/8 Examples thereof include swellable mica such as Mg _2/5 Li _1/8 (Si ₄ O ₁₀ ) F ₂ . In addition, synthetic smectites are also useful.

In the present invention, among the above-described mica compounds, fluorine-based swellable mica is particularly useful. That is, this swellable synthetic mica has a laminated structure composed of unit crystal lattice layers having a thickness of about 1 to 1.5 nm, and the substitution of metal atoms in the lattice is significantly larger than other viscosity minerals. As a result, the lattice layer is deficient in positive charge, and in order to compensate for this, cations such as Li ⁺ , Na ⁺ , Ca ²⁺ , and Mg ²⁺ are adsorbed between the layers. The cations present between these layers are called exchangeable cations and exchange with various cations. In particular, when the cation between the layers is Li ⁺ or Na ⁺ , the bond between the layered crystal lattices is weak because the ionic radius is small, and the layer swells greatly with water. If shear is applied in this state, it will easily cleave and form a stable sol in water. Swellable synthetic mica has a strong tendency and is useful in the present invention. In particular, swellable synthetic mica is preferably used.

  The shape of the mica compound is preferably as small as possible from the viewpoint of diffusion control, and the plane size is preferably as long as the smoothness of the coated surface and the transmittance of actinic rays are not impaired. Accordingly, the aspect ratio is 20 or more, preferably 100 or more, particularly preferably 200 or more. The aspect ratio is the ratio of the thickness to the major axis of the particle, and can be measured from, for example, a projected view of the particle by a micrograph. The larger the aspect ratio, the greater the effect that can be obtained.

  The average major axis of the mica compound is preferably 0.3 to 20 μm, more preferably 0.5 to 10 μm, and particularly preferably 1 to 5 μm. Further, the average thickness of the mica compound is preferably 0.1 μm or less, more preferably 0.05 μm or less, and particularly preferably 0.01 μm or less. Specifically, for example, the swellable synthetic mica that is a representative compound has a thickness of 1 to 50 nm and a surface size (major axis) of about 1 to 20 μm.

  The amount contained in the oxygen-blocking layer of the inorganic stratiform compound, which is a preferred example of a mica compound, includes the suppression of adhesion between laminated lithographic printing plate precursors, suppression of scratches, and sensitivity due to blocking during laser exposure. From the viewpoint of reduction, low oxygen permeability, etc., it is preferably in the range of 5 to 50% by mass, particularly preferably in the range of 10 to 40% by mass, based on the total solid content of the oxygen barrier layer. Even when a plurality of kinds of inorganic layered compounds are used in combination, the total amount of these inorganic layered compounds is preferably the above-described mass ratio.

(Oxygen permeability control agent)
As one method for controlling oxygen permeability in the protective layer, there is a method of mixing other water-soluble polymer as an oxygen permeability control agent together with polyvinyl alcohol suitable as a binder polymer.

Other water-soluble polymers include polyvinylpyrrolidone, polyethylene glycol, soluble starch, carboxymethylcellulose, hydroxyethylcellulose, ethylene oxide and propylene oxide copolymer compounds.
Of these, compounds represented by the following general formula (A) are preferred.

（一般式（Ａ）中、ａは、１〜１００までの整数を表し、ｂは１〜１００までの整数を表し、ｃは１〜１００までの整数を表す。）

(In general formula (A), a represents an integer from 1 to 100, b represents an integer from 1 to 100, and c represents an integer from 1 to 100.)

  As content of the oxygen permeability control agent in an oxygen barrier layer, 0.5-20 mass% is preferable with respect to solid content mass of the whole oxygen permeable layer, and 1-10 mass% is more preferable.

(Formation of oxygen barrier layer)
The oxygen-blocking layer in the present invention is formed by applying an oxygen-blocking layer coating solution containing each component contained in the layer onto a photosensitive layer described later.

  Known additives such as a surfactant for improving the coating property and a water-soluble plasticizer for improving the physical properties of the film can be added to the coating solution for the oxygen barrier layer. Examples of the water-soluble plasticizer include propionamide, cyclohexanediol, glycerin, sorbitol and the like. A water-soluble (meth) acrylic polymer can also be added. Furthermore, a known additive for improving the adhesion with the layer provided on the support side of the oxygen barrier layer and the aging stability of the coating solution may be added to the coating solution.

  The coating method of the oxygen barrier layer according to the present invention is not particularly limited, and the method described in US Pat. No. 3,458,311 or JP-A-55-49729 is applied. be able to.

The coating amount of the oxygen barrier layer is 0.1 to 4.0 g / m ^{2 from} the viewpoint of maintaining appropriate oxygen permeability for exhibiting film strength, scratch resistance, image quality, and safelight suitability. Preferably, 0.3 to 3.0 g / m ² is more preferable.

(Back coat layer)
In the lithographic printing plate precursor according to the invention, a backcoat layer can be provided on the other surface (the non-photosensitive layer side) of the support provided with a photosensitive layer sensitive to laser light. In this case, Ra in the present invention means Ra on the surface of the backcoat layer. The means for reducing Ra to 0.15 μm or less is not particularly limited. In particular, after the Ra of aluminum is reduced to 0.15 or less by the above-described method, the backcoat layer is applied or the amount of the backcoat layer applied is constant. The method of adjusting to the value (preferable coating amount shown later) is mentioned. In particular, a method of providing a back coat layer after making the average surface roughness (Ra) of aluminum 0.15 μm or less by the above method is preferable.
Hereinafter, the back coat layer will be described.
The back coat layer applicable to the present invention is a layer mainly composed of a resin having a film forming property, and can contain various additives as necessary.

[Resin that can be used for the back coat layer]
As the resin that can be used for the back coat layer in the present invention, those having film formation can be appropriately selected and used. For example, polyethylene, polypropylene, polybutene, polyamide (trademark: nylon), polybutadiene, polyurethane, polyurea, Polyimide, polysiloxane, polycarbonate, polyester, epoxy resin, alkylphenol aldehyde condensation resin, polyacetal, polybutyral, polyvinyl chloride, polyvinylidene chloride, polystyrene, resins having phenolic hydroxyl groups, acrylic resins and copolymer resins thereof, Examples include hydroxy cellulose, polyvinyl alcohol, cellulose acetate, carboxymethyl cellulose and the like. Among these, polyesters, resins having a phenolic hydroxyl group, and polyacetals are particularly preferable from the viewpoints of film properties and adhesion resistance to the outermost surface on the photosensitive recording layer side.
The weight average molecular weight of these other resins is preferably 500 or more, more preferably 1,000 to 500,000, still more preferably 1,000 to 200,000, and more preferably 1,000 to 100,000 in terms of polystyrene. Particularly preferred.

Hereinafter, typical resins that can be used for the overcoat layer will be described in detail.
-Polyester resin-
The polyester resin is composed of a dicarboxylic acid unit and a diol unit.
Dicarboxylic acid units include aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, tetrabromophthalic acid, tetrachlorophthalic acid; adipic acid, azelaic acid, succinic acid, succinic acid, suberic acid, sebacic acid, malonic acid And saturated aliphatic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid.
Diol units include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 1,4-butylene glycol, neopentyl. Aliphatic chain diols such as glycol, hexanediol, 2,2,4-trimethyl-1,3-pentanediol; 1,4-bis-β-hydroxyethoxycyclohexane, cyclohexanedimethanol, tricyclodecane dimethanol, bisphenol And cyclic diols such as dioxyethyl ether and bisphenol dioxypropyl ether.
These dicarboxylic acid and diol units are each preferably at least one, and either one is preferably used as two or more copolymer units, and the properties of the copolymer are determined by the copolymer composition and molecular weight.
As the polyester resin, a commercially available product can be used. For example, Chemit 1294 (trade name) manufactured by Toray Industries, Inc. is a suitable example.

  As will be described later, the back coat layer in the present invention is preferably formed by application from a solution in order to efficiently provide a thin layer. Accordingly, the polyester resin that can be used for forming the backcoat layer is preferably non-crystalline and easily soluble in various industrial organic solvents.

-Polyacetal resin-
The polyacetal resin is a resin obtained by acetalizing polyvinyl alcohol with an aldehyde such as butyraldehyde or formaldehyde. The polyacetal resin has different physical and chemical properties depending on the degree of acetalization, the composition ratio of hydroxyl groups and acetyl groups, and the degree of polymerization. For the back coat layer in the present invention, a resin having an acetalization degree of 60 mol% or more, an acetyl group of 5 mol% or less, and a polymerization degree of 300 or more is preferably used.
As a polyacetal resin, a commercial item can also be used, for example, Sleksui BX-1 manufactured by Sekisui Chemical Co., Ltd., ESREC BX-3, ESREC BX-5, ESREC KS-1, ESREC KS-3, ESREC KS. -5, ESREC KS-10, and the like.

-Resin having phenolic hydroxyl group-
Examples of the resin having a phenolic hydroxyl group include a condensation polymer of phenol and formaldehyde, a condensation polymer of m-cresol and formaldehyde, a condensation polymer of p-cresol and formaldehyde, and m- / p-mixed cresol. A condensation polymer of formaldehyde, a novolak resin such as a condensation polymer of phenol and cresol (m-, p- or m- / p-mixed) and formaldehyde, or a condensation polymer of pyrogallol and acetone. The pyrogallol resin which is can be mentioned.

Moreover, the copolymer which copolymerized the compound which has a phenolic hydroxyl group can also be used as resin which has a phenolic hydroxyl group.
Here, examples of the compound having a phenolic hydroxyl group include acrylamide, methacrylamide, acrylic acid ester, methacrylic acid ester, and hydroxystyrene having a phenolic hydroxyl group.
Among these resins, polyesters, polyacetals, resins having phenolic hydroxyl groups, and the like are preferable.

(Other ingredients)
In the backcoat layer in the present invention, a plasticizer, a surfactant, and other additives can be added as necessary for the purpose of imparting flexibility to the backcoat layer and adjusting slipperiness. Hereinafter, additives that can be used in the backcoat layer will be described.

-Plasticizer-
Preferred plasticizers that can be used in the backcoat layer include, for example, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, octyl capryl phthalate, dicyclohexyl phthalate, ditridecyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, diallyl phthalate, and the like. Phthalates, dimethyl glycol phthalate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, glycol esters such as triethylene glycol dicaprylate, tricresyl phosphate, triphenyl Phosphate esters such as phosphate, diisobutyl adipate, dioctyl adipate, Methyl sebacate, dibutyl sebacate, dioctyl azelate, aliphatic dibasic acid esters such as dibutyl maleate, poly glycidyl methacrylate, triethyl citrate, glycerin triacetyl ester, and butyl laurate is effective.
These plasticizers are added as long as the back coat layer is not sticky. The addition amount can be determined according to the properties of the resin as the main component and the required flexibility, but when using a novolak resin or pyrogallol resin having a phenolic hydroxyl group as a representative resin, A preferable addition amount is preferably 0.1 to 20% by mass in terms of solid matter in the coating solution.

-Surfactant-
Preferred examples of the surfactant that can be used in the back coat layer include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene polystyryl phenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, glycerin. Fatty acid partial esters, sorbitan fatty acid partial esters, pentaerythritol fatty acid partial esters, propylene glycol mono fatty acid esters, sucrose fatty acid partial esters, polyoxyethylene sorbitan fatty acid partial esters, polyoxyethylene sorbitol fatty acid partial esters, polyethylene Glycol fatty acid esters, polyglycerin fatty acid partial esters, polyoxyethylenated castor oil, polyoxyethylene glycerin fat Partial esters, fatty acid diethanolamides, N, N
-Nonionic surfactants such as bis-2-hydroxyalkylamines, polyoxyethylene alkylamines, triethanolamine fatty acid esters, trialkylamine oxides, fatty acid salts, abietic acid salts, hydroxyalkane sulfonates, alkane sulfones Acid salts, dialkyl sulfosuccinate esters, linear alkyl benzene sulfonates, branched alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkylphenoxy polyoxyethylene propyl sulfonates, polyoxyethylene alkyl sulfophenyl ether salts, N -Methyl-N-oleyl taurine sodium salt, N-alkylsulfosuccinic acid monoamide disodium salt, petroleum sulfonates, sulfated beef oil, sulfurized fatty acid alkyl ester Ester salt, alkyl sulfate ester salt, polyoxyethylene alkyl ether sulfate ester salt, fatty acid monoglyceride sulfate ester salt, polyoxyethylene alkyl phenyl ether sulfate ester salt, polyoxyethylene styryl phenyl ether sulfate ester salt, alkyl phosphate ester salt, poly Oxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates, partially saponified styrene / maleic anhydride copolymers, partially saponified olefin / maleic anhydride copolymers, naphthalene sulfone Anionic surfactants such as acid salt formalin condensates, alkylamine salts, quaternary ammonium salts, polyoxyethylene alkylamine salts, polyethylene polyamine derivatives Cationic surfactants such as body, carboxy betaines, aminocarboxylic acids, sulfobetaines, amino sulfate esters, amphoteric surfactants such as imidazolines such.
Among the surfactants listed above, those having polyoxyethylene can be read as polyoxyalkylenes such as polyoxymethylene, polyoxypropylene and polyoxybutylene, and these surfactants are also included.

  A more preferred surfactant is a fluorosurfactant containing a perfluoroalkyl group in the molecule. Such fluorosurfactants include perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, anionic types such as perfluoroalkyl phosphates, amphoteric types such as perfluoroalkyl betaines, and perfluoroalkyltrimethylammonium salts. Cationic and perfluoroalkyl amine oxides, perfluoroalkyl ethylene oxide adducts, perfluoroalkyl group and hydrophilic group-containing oligomers, perfluoroalkyl group and lipophilic group-containing oligomers, perfluoroalkyl groups, hydrophilic groups and lipophilic groups Nonionic types such as group-containing oligomers, perfluoroalkyl groups, and lipophilic group-containing urethanes can be mentioned.

  Said surfactant can be used individually or in combination of 2 or more types, Preferably it is 0.001-10 mass% in a backcoat layer, More preferably, it is the range of 0.001-5 mass%. Added.

  The backcoat layer in the present invention further includes an o-naphthoquinone diazide compound, a photosensitive azide compound, a photopolymerizable composition containing an unsaturated double bond-containing monomer as a main component, and a photocrosslinking containing cinnamic acid or a dimethylmaleimide group. Chemical compounds and diazo resins obtained by condensing diazonium salt monomers and aromatic diazonium salts with reactive carbonyl group-containing organic condensing agents (especially aldehydes or acetals such as formaldehyde and acetaldehyde) in an acidic medium. It can be added for improvement. Of these, o-naphthoquinonediazide compounds known as positive photosensitive compounds are preferably used.

-Formation of backcoat layer-
The backcoat layer in the present invention can be provided by thermocompression bonding of a film, a melt lamination method, or a coating method. Application from a solution is more preferable for efficiently providing a thin layer.
Accordingly, in the present invention, the resin used for the backcoat layer is preferably non-crystalline and easily soluble in various industrial organic solvents.

Solvents used in forming the backcoat layer include seton, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, Propylene glycol monoethyl ether, acetylacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethyleneglycol Monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, methyl lactate And ethyl lactate.
These solvents can be used alone or in combination. The concentration of the solid content in the backcoat layer forming coating solution is suitably 0.5 to 50% by mass.

The coverage of the backcoat layer in the invention is preferably in the range of 0.01 to 10 g / ^{m 2} by mass after drying, more preferably in the range of 0.05~7g / ^{m 2,} 0.1~5g / ^m The range of ² is more preferable, and the range of 0.3 to 0.8 g / m ² is most preferable.

(Bekk smoothness)
The planographic printing plate precursor of the present invention has a Bekk smoothness of 10,000 seconds on the surface sensitive to the laser beam of the planographic printing plate precursor from the viewpoint of ensuring transportability with a setter when laminated without interposing the interleaving paper. Or less, more preferably 5,000 seconds or less. By selecting the type, content, particle size, and the like of the filler that can be contained in the protective layer, it is possible to control within the above range.
Here, “Bekk smoothness of the surface sensitive to laser light” represents the Bekk smoothness of the outermost surface on the side where the photosensitive layer is present on the support surface. For example, when only the photosensitive layer is provided on the surface of the support, the Bekk smoothness of the surface of the photosensitive layer is represented, and when the protective layer is provided on the photosensitive layer, the Bekk smoothness of the surface of the protective layer is represented.
Bekk smoothness is expressed in the time (seconds) required for a certain amount of atmospheric pressure air to flow between a test piece brought into contact under a specific condition and a ring-shaped plane under a specific initial differential pressure. The As a method for measuring Bekk smoothness on the outermost surface on the protective layer side, a method described in JIS P 8119, ISO 5627 (1995) is used. The measurement was performed using a Beck smoothness tester manufactured by Kumagai Riki Kogyo Co., Ltd., with an air amount of 1/10 of the standard air amount, that is, 1 cc. The Bekk smoothness in the claims of the present application is a value obtained by this measuring method.

<Laminated body of lithographic printing plate precursor>
The laminate of the lithographic printing plate precursor according to the invention is characterized in that a plurality of the lithographic printing plate precursors according to the invention are laminated in direct contact with the uppermost layer of the lithographic printing plate precursor according to the invention. Such a laminate generally takes the form of state 10 ″ in FIG.
In the laminate of the lithographic printing plate precursor according to the present invention, since the generation of scratches between the photosensitive layer or protective layer surface and the back surface of the aluminum support is effectively suppressed, the conventional lithographic printing plate precursor laminate In this way, it is not necessary to insert a slip sheet that has a function of preventing adhesion between planographic printing plate precursors and a function of preventing scratches caused by rubbing with an aluminum support. Moreover, since the occurrence of defective products due to scratches and the like is also suppressed, productivity can be improved.

[Plate making of lithographic printing plate precursor]
In order to make a lithographic printing plate precursor according to the present invention, at least exposure and development processes are performed.
As a light source for exposing the negative planographic printing plate precursor of the present invention, a known light source can be used without limitation. The wavelength of a desirable light source is 300 nm to 1200 nm, and specifically, it is preferable to use various lasers as the light source, and among them, an infrared laser having a wavelength of 780 nm to 1200 nm is preferably used.
The exposure mechanism may be any of an internal drum system, an external drum system, a flat bed system, and the like.

  In addition, as other exposure beams for the lithographic printing plate precursor of the present invention, ultra-high pressure, high pressure, medium pressure, low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, various visible and ultraviolet laser lamps Fluorescent lamps, tungsten lamps, sunlight, etc. can also be used.

The lithographic printing plate precursor according to the invention is developed after being exposed. In such development processing, distilled water, an alkaline aqueous solution having a pH of 14 or less, or washing water, a surfactant and the like described in JP-A Nos. 54-8002, 55-11545, and 59-58431 are contained. Rinsing liquid, desensitizing liquid containing gum arabic or starch derivatives can be used.
As the developer, an alkaline aqueous solution having a pH of 14 or less is particularly preferable, and an alkaline aqueous solution having a pH of 8 to 12 containing an anionic surfactant is more preferably used. For example, tribasic sodium phosphate, potassium, ammonium, dibasic sodium phosphate, potassium, ammonium, sodium carbonate, potassium, ammonium, sodium bicarbonate, potassium, ammonium, sodium borate, Examples include inorganic alkaline agents such as potassium, ammonium, sodium hydroxide, ammonium, potassium and lithium. Moreover, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, Organic alkali agents such as ethyleneimine, ethylenediamine, and pyridine are also used. These alkali agents are used alone or in combination of two or more.

In the development processing of the lithographic printing plate precursor according to the invention, 1 to 20% by mass of an anionic surfactant is added to the developer, and more preferably 3 to 10% by mass. If the amount is too small, the developability deteriorates. If the amount is too large, the strength such as the abrasion resistance of the image deteriorates. Anionic surfactants include, for example, sodium salt of lauryl alcohol sulfate, ammonium salt of lauryl alcohol sulfate, sodium salt of octyl alcohol sulfate, such as sodium salt of isopropyl naphthalene sulfonic acid, sodium salt of isobutyl naphthalene sulfonic acid, polyoxy Higher carbon number such as sodium salt of ethylene glycol mononaphthyl ether sulfate ester, sodium salt of dodecylbenzene sulfonic acid, alkylaryl sulfonate such as sodium salt of metanitrobenzene sulfonic acid, secondary sodium alkyl sulfate, etc. Aliphatic alcohol phosphates such as alcohol sulfates, sodium salts of cetyl alcohol phosphates, eg C _{17 H 33 CON (CH 3)} CH 2 CH 2 SO 3 sulfonates of alkylamides such as Na, for example, sodium sulfosuccinate dioctyl ester, sulfonate of dibasic aliphatic esters such as sodium sulfosuccinate dihexyl ester Salts are included.

  If necessary, an organic solvent such as benzyl alcohol mixed with water may be added to the developer. As the organic solvent, those having a solubility in water of about 10% by mass or less are suitable, and preferably selected from those having 5% by mass or less. For example, 1-phenylethanol, 2-phenylethanol, 3-phenylpropanol, 1,4-phenylbutanol, 2,2-phenylbutanol, 1,2-phenoxyethanol, 2-benzyloxyethanol, o-methoxybenzyl alcohol, m -Methoxybenzyl alcohol, p-methoxybenzyl alcohol, benzyl alcohol, cyclohexanol, 2-methylcyclohexanol, 4-methylcyclohexanol, 3-methylcyclohexanol and the like can be mentioned. The content of the organic solvent is preferably 1 to 5% by mass with respect to the total mass of the developer at the time of use. The amount used is closely related to the amount of surfactant used, and it is preferable to increase the amount of anionic surfactant as the amount of organic solvent increases. This is because when the amount of the organic solvent is large and the amount of the anionic surfactant is small, the organic solvent is not dissolved, so that it is impossible to expect good developability.

Furthermore, additives such as an antifoaming agent and a hard water softening agent can be further contained as necessary. Examples of the hard water softener include Na ₂ P ₂ O ₇ , Na ₅ P ₃ O ₃ , Na ₃ P ₃ O ₉ , Na ₂ O ₄ P (NaO ₃ P) PO ₃ Na ₂ , and Calgon (sodium polymetaphosphate). Such as polyphosphates, aminopolycarboxylic acids (eg, ethylenediaminetetraacetic acid, its potassium salt, its sodium salt; diethylenetriaminepentaacetic acid, its potassium salt, its sodium salt; triethylenetetraminehexaacetic acid, its potassium salt, its sodium salt Hydroxyethylethylenediaminetriacetic acid, its potassium salt, its sodium salt; nitrilotriacetic acid, its potassium salt, its sodium salt; 1,2-diaminocyclohexanetetraacetic acid, its potassium salt, its sodium salt; 1,3-diamino-2 -Propanol tetraacetic acid , Its potassium salt, its sodium salt), other polycarboxylic acids (for example, 2-phosphonobutanetricarboxylic acid-1,2,4, its potassium salt, its sodium salt; 2 monophosphonobutanone tricarboxylic acid-2, 3,4, its potassium salt, its sodium salt, etc.), organic phosphonic acids (eg, 1-phosphonoethanetricarboxylic acid-1,2,2, its potassium salt, its sodium salt; 1-hydroxyethane-1,1 -Diphosphonic acid, its potassium salt, its sodium salt; aminotri (methylenephosphonic acid), its potassium salt, its sodium salt, etc.). The optimum amount of such a hard water softener varies depending on the hardness of the hard water used and the amount used, but is generally 0.01 to 5% by weight, more preferably in the developer at the time of use. It is made to contain in 0.01-0.5 mass%.

  Further, when the lithographic printing plate precursor of the present invention is developed using an automatic developing machine, the developing solution becomes fatigued according to the processing amount, so that the replenishing solution or a fresh developing solution is used to increase the processing capacity. It may be recovered. In this case, it is preferable to replenish by the method described in US Pat. No. 4,882,246. Developers described in JP-A-50-26601, 58-54341, JP-B-56-39464, 56-42860, and 57-7427 are also preferable.

  The lithographic printing plate precursor thus developed is subjected to washing water, surface activity as described in JP-A Nos. 54-8002, 55-11545, 59-58431, and the like. It may be post-treated with a rinsing liquid containing an agent, a desensitizing liquid containing gum arabic, starch derivatives, and the like. These treatments can be used in various combinations for the post-treatment of the lithographic printing plate precursor according to the invention.

As the plate-making process of the lithographic printing plate precursor according to the invention, the entire surface may be heated before exposure, during exposure, and between exposure and development, if necessary. By such heating, the image forming reaction in the photosensitive layer is promoted, and advantages such as improvement in sensitivity and printing durability and stabilization of sensitivity may occur. Further, for the purpose of improving the image strength and printing durability, it is also effective to subject the developed image to full post heating or full exposure.
Usually, heating before development is preferably performed under mild conditions of 150 ° C. or less from the viewpoint of occurrence of an undesired curing reaction. Also, very strong conditions can be used for heating after development. Usually, the heating temperature is in the range of 200 to 500 ° C. from the viewpoint of image strengthening action and thermal decomposition of the image area.

The planographic printing plate obtained by the above processing is loaded on an offset printing machine and used for printing a large number of sheets.
The stain resistance of the lithographic printing plate subjected to printing can be removed by a plate cleaner. As plate cleaners used for removing stain resistance on printing plates, conventionally known plate cleaners for PS plates are used. For example, CL-1, CL-2, CP, CN-4, CN CG-1, PC-1, SR, IC (manufactured by Fuji Photo Film Co., Ltd.) and the like.

Hereinafter, the present invention will be described by way of examples, but the present invention is not limited thereto.
In the following examples, a photosensitive lithographic printing plate precursor which is a preferred embodiment thereof is prepared and evaluated as the lithographic printing plate precursor of the present invention.

[Example 1]
In addition to aluminum, a molten aluminum alloy containing the following elements (hereinafter, appropriately referred to as “Al molten metal”) was prepared.
Si: 0.06% by weight
Fe: 0.30% by weight
Cu: 0.017% by weight
Mn: 0.001% by weight
Mg: 0.001% by weight
Zn: 0.001% by weight
Ti: 0.03% by weight

  After cleaning with the molten aluminum filtration, an ingot having a thickness of 500 mm and a width of 1200 mm was produced by a DC casting method. The surface of the obtained ingot was scraped off with a chamfering machine with an average of 10 mm. Thereafter, the temperature was maintained at 550 ° C. for about 5 hours, and when the temperature dropped to 400 ° C., a rolled sheet having a thickness of 2.7 mm was formed using a hot rolling mill. Further, after heat treatment was performed at 500 ° C. using a continuous annealing machine, an aluminum alloy plate having a thickness of 0.24 mm was obtained using a cold rolling mill. Using rolls with various surface roughness as the rolling roll of the cold rolling mill, performing cold rolling, the average of the back surface of the aluminum alloy plate (the surface opposite to the surface on which the photosensitive layer is formed) Aluminum alloy plates with various roughnesses were produced.

Next, the surface of various aluminum alloy plates (the surface on which the surface roughness was not adjusted in the cold rolling process) was subjected to an alkali etching process (the amount of aluminum dissolved was 5.5 g / m ² ), and then continued. Desmutting treatment with nitric acid spray was performed. An AC electrolytic surface roughening treatment was performed at an electric quantity of 270 C / dm ² to roughen the surface. Thereafter, alkali etching treatment (amount of aluminum dissolved was 0.2 g / m ² ) and desmut treatment by nitric acid spray were performed again. Furthermore, an anodized film was formed on the front and back surfaces of the aluminum alloy plate using an anodizing apparatus having the same configuration as shown in FIG. 4 (surface film amount: 2.6 g / m ² , back film amount: 0.1 g / m ² ). Thereafter, an interface treatment was performed using sodium silicate. In this manner, supports each having various values of the average surface roughness in the width direction and the longitudinal direction of the back surface were prepared. The results are shown in Table 1.

<Undercoat layer>
Next, the following undercoat layer coating solution was applied to the aluminum support with a wire bar and dried at 90 ° C. for 30 seconds. The coating amount was 10 mg / m ² .

(Coating solution for undercoat layer)
-Polymer compound A having the following structure: 0.05 g
・ Methanol 27g
・ Ion exchange water 3g

(Photosensitive layer)
Next, the following photosensitive layer coating solution [P-1] was prepared and applied to the above aluminum support using a wire bar. Drying was performed at 115 ° C. for 34 seconds with a hot air dryer to obtain a lithographic printing plate precursor. The coating amount after drying was 1.36 g / m ² .

<Photosensitive layer coating solution [P-1]>
・ Infrared absorbing dye (IR-1) 0.074g
-Polymerization initiator (OS-12) 0.280g
・ Additive (PM-1) 0.151g
・ Polymerizable compound (AM-1) 1.00 g
・ Specific binder polymer (BT-1) 1.00g
・ Ethyl violet (C-1) 0.04g
・ Fluorine-based surfactant 0.015g
(Megafac F-780-F Dainippon Ink & Chemicals, Inc., methyl isobutyl ketone (MIBK) 30% by mass solution)
・ Methyl ethyl ketone 10.4g
・ Methanol 4.83g
・ 10.4 g of 1-methoxy-2-propanol

In addition, the polymerization initiator (OS-12) used for the said photosensitive layer coating liquid refers to what is mentioned as a compound example of the onium salt represented by the above-mentioned general formula (1).
In addition, the structures of the infrared-absorbing dye (IR-1), additive (PM-1), polymerizable compound (AM-1), binder polymer (BT-1), and ethyl violet (C-1) are shown below. .

(Protective layer)
On the surface of the oxygen barrier layer, polyvinyl alcohol (Goceran CKS-50: degree of saponification 99 mol%, degree of polymerization 300, sulfonic acid-modified polyvinyl alcohol manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) and surfactant (manufactured by Nippon Emulsion Co., Ltd., Emma Rex 710) and filler (Chemipearl W-308, high-density polyethylene particle 40% aqueous dispersion with 6 μm particle diameter, manufactured by Mitsui Chemicals, Inc.) are applied with a wire bar. Then, it was dried at 125 ° C. for 75 seconds with a warm air dryer. The content ratio of the filler / polyvinyl alcohol / surfactant after drying in this mixed aqueous solution (protective layer coating solution) is 2.5 / 93 / 4.5 (mass%), and the total coating amount is (Coating amount after drying) was 1.60 g / m ² .
Further, the Bekk smoothness of the protective layer on the surface of the support produced as described above was 125 seconds.

  The obtained lithographic printing plate precursors were sequentially stacked in the same direction without interleaving of the slip sheet to obtain a laminate of lithographic printing plate precursors.

[Examples 2 to 5]
In Examples 2 to 5, a lithographic printing plate precursor laminate was obtained in the same manner as in Example 1 except that a support whose average surface roughness in the width direction and longitudinal direction on the back side of the support was shown in Table 1 was used.

[Examples 6 to 10]
Synthetic mica (Somasif MEB-3L, in place of the filler (Chemipearl W-308, high-density polyethylene particle 40% aqueous dispersion with a particle size of 6 μm, manufactured by Mitsui Chemicals, Inc.) in the protective layer of Examples 1 to 5 Lithographic printing plate precursors of Examples 6 to 10 were obtained in the same manner as Examples 1 to 5 except that 3.2% aqueous dispersion (manufactured by Coop Chemical Co., Ltd.) was added.
The content ratio of the synthetic mica / polyvinyl alcohol / surfactant after drying in this mixed aqueous solution (protective layer coating solution) is 12 / 83.5 / 4.5 (mass%), and the total coating amount. (Coating amount after drying) was 1.60 g / m ²

Example 11
First, synthesis examples of (B) a polymer having a phenyl group substituted with a vinyl group in the side chain and (C) a monomer having two or more phenyl groups substituted with a vinyl group are shown below. .

[Synthesis Example 1: (B) Synthesis Example of Specific Polymer (P-1)]
150 g of bismuthiol (2,5-dimercapto-1,3-4-thiadiazole) was suspended in 600 ml of methanol, and 101 g of triethylamine was gradually added while cooling to obtain a uniform solution. While maintaining at room temperature, p-chloromethylstyrene (manufactured by Seimi Chemical Co., CMS-14) was added dropwise over 10 minutes, and stirring was further continued for 3 hours. The reaction product gradually precipitated. After stirring, the reaction product was transferred to an ice bath, the internal temperature was cooled to 10 ° C., and the product was separated by suction filtration. The compound (monomer) shown below was obtained with a yield of 75% by washing with methanol and drying for one day in a vacuum dryer.

  40 g of the above monomer is placed in a 1-liter four-necked flask equipped with a stirrer, a nitrogen inlet tube, a thermometer, and a reflux condenser, 70 g of methacrylic acid, 200 ml of ethanol and 50 ml of distilled water are added, and triethylamine is stirred on a water bath. 110 g was added. Under nitrogen atmosphere, the internal temperature was heated to 70 ° C., and 1 g of azobisisobutyronitrile (AIBN) was added at this temperature to initiate polymerization. The mixture was heated and stirred for 6 hours, and then the polymerization system was cooled to room temperature. A part of the sample was taken out, diluted hydrochloric acid was added to adjust the pH to about 3, and this was poured into water to obtain a polymer having the structure shown below.

  100 g of 1,4-dioxane and 23 g of p-chloromethylstyrene were added to the remaining polymer solution from which a part of the polymer was taken out, and stirring was further continued at room temperature for 15 hours. Thereafter, 80 to 90 g of concentrated hydrochloric acid (35 to 37% aqueous solution) was added, and after confirming that the pH of the system was 4 or less, the whole was transferred into 3 liters of distilled water. The precipitated polymer was separated by filtration, washed repeatedly with distilled water, and then dried for one day in a vacuum dryer. Thereby, the target (B) specific polymer (P-1) was obtained with a yield of 90%. It is a polymer having a weight average molecular weight of 90,000 (polystyrene conversion) by molecular weight measurement by gel permeation chromatography, and further supports the structure of (B) specific polymer (P-1) by analysis by proton NMR. there were.

[Synthesis Example 2: (C) Synthesis Example of Specific Monomer (C-5)]
A thirocyanuric acid 89g was suspended in 1.5 liters of methanol, and a 30% aqueous solution in which 84 g of potassium hydroxide was dissolved was gradually added while cooling to obtain a uniform solution. To this, 230 g of p-chloromethylstyrene was gradually added dropwise at room temperature so that the internal temperature did not exceed 40 ° C. Shortly after the addition, the product precipitated, but the stirring was continued, and after stirring for 3 hours, the product was separated by suction filtration. After washing with methanol and drying all day and night in a vacuum dryer, (C) the specific monomer (C-5) was obtained in a yield of 90%.

(Production of support)
By polishing one side of a JIS A 1050 aluminum plate having a thickness of 0.30 mm and a width of 1030 mm by buffing, the average surface roughness Ral in the width direction is 0.13 μm and the average surface roughness Ras in the longitudinal direction is 0.10 μm. A support was obtained. The polished surface was used as the back surface, and the following surface treatment was performed on the opposite surface.

<Surface treatment>
In the surface treatment, the following various treatments (a) to (f) were continuously performed. In addition, after each process and water washing, the liquid was drained with the nip roller.

(A) The aluminum plate was etched at a caustic soda concentration of 26 mass%, an aluminum ion concentration of 6.5 mass%, and a temperature of 70 ° C. to dissolve the aluminum plate by 5 g / m ² . Thereafter, it was washed with water.
(B) A desmut treatment by spraying was performed with a 1% by mass aqueous solution of nitric acid having a temperature of 30 ° C. (including 0.5% by mass of aluminum ions), and then washed with water.

(C) An electrochemical surface roughening treatment was continuously performed using an alternating voltage of 60 Hz. The electrolytic solution at this time was a 1% by mass aqueous nitric acid solution (including 0.5% by mass aluminum ions and 0.007% by mass ammonium ions) at a temperature of 30 ° C. The AC power source was subjected to an electrochemical surface roughening treatment using a carbon electrode as a counter electrode using a trapezoidal rectangular wave alternating current with a time TP of 2 msec until the current value reached a peak from zero and a duty ratio of 1: 1. Ferrite was used for the auxiliary anode. The current density was 25 A / dm ² at the current peak value, and the amount of electricity was 250 C / cm ² in terms of the total amount of electricity when the aluminum plate was the anode. 5% of the current flowing from the power source was shunted to the auxiliary anode. Thereafter, it was washed with water.

(D) The aluminum plate was etched by spraying at 35 ° C. with a caustic soda concentration of 26% by mass and an aluminum ion concentration of 6.5% by mass, the aluminum plate was dissolved at 0.2 g / m ² , and electricity was obtained using the previous AC. The removal of the smut component mainly composed of aluminum hydroxide generated during chemical roughening and the edge portion of the generated pit were dissolved to smooth the edge portion. Thereafter, it was washed with water.
(E) A desmut treatment by spraying was performed with a 25% by weight aqueous solution of sulfuric acid having a temperature of 60 ° C. (containing 0.5% by weight of aluminum ions), followed by washing with water by spraying.

(F) Anodization was performed for 50 seconds at a sulfuric acid concentration of 170 g / liter (containing 0.5 mass% of aluminum ions), a temperature of 33 ° C., and a current density of 5 (A / dm ² ). Thereafter, it was washed with water. The amount of the anodized film at this time was 2.7 g / m ² .

  The surface roughness Ra, surface area ratio ΔS, and steepness a45 of the aluminum support thus obtained were Ra = 0.27 (measuring instrument: Surfcom manufactured by Tokyo Seimitsu Co., Ltd., stylus tip diameter 2 microns), respectively. Meter), ΔS = 75%, a45 = 44% (measuring instrument: SPA300 / SPI3800N manufactured by Seiko Instruments Inc.).

[Formation of negative photosensitive layer]
Next, the following photosensitive layer coating solution is prepared, applied to the aluminum support subjected to the above surface treatment so that the thickness after drying becomes 1.4 μm, and dried in a dryer at 70 ° C. for 5 minutes. The lithographic printing plate precursor was obtained.

<Photosensitive layer coating solution>
-(A) Radical generator (BC-6) 2.5 parts by mass-(B) Specific polymer (P-1) 10.0 parts by mass-(C) Specific monomer (C-5) 3.5 parts by mass (D) Infrared absorbing dye (S-4) 0.5 part by mass Dioxane 70.0 part by mass Cyclohexane 20.0 part by mass

  The (B) and (C) are the compounds shown in Synthesis Example 1 and Synthesis Example 2. Said (A) and (D) are the compounds shown below. The obtained lithographic printing plate precursors were sequentially stacked in the same direction without interleaving of the slip sheets, and a lithographic printing plate precursor laminate was obtained.

Example 12
In Example 1, the average surface roughness (Ral) in the width direction of the back surface of the support obtained by changing the buffing conditions of the support was 0.13 μm, and the average surface roughness (Ras) in the longitudinal direction was 0.1. Using a 10 μm support, a highly sensitive photopolymerizable composition P-1 having the following composition was applied on the undercoat layer described in Example 1 so that the coating amount after drying was 1.4 g / m ^2. And dried at 100 ° C. for 1 minute to form a photosensitive layer.
The obtained lithographic printing plate precursors were sequentially stacked in the same direction without interleaving of the slip sheet to obtain a laminate of lithographic printing plate precursors.

(Photopolymerizable composition P-1)
Polymerizable compound (A-1) 4.2 parts by mass Binder polymer (B-1) 3.6 parts by mass Sensitizing dye (C-1) 0.21 parts by mass Polymerization initiator (D-1) 0.81 part by mass, chain transfer agent (E-1) 0.3 part by mass, dispersion of ε-phthalocyanine pigment 0.76 part by mass (pigment: 15 parts by mass, dispersant allyl methacrylate / methacrylic acid copolymer ( Copolymerization molar ratio 83/17): 10 parts by mass, cyclohexanone: 15 parts by mass)
・ 0.05 parts by mass of fluorine-based nonionic surfactant Megafac F780 (Dainippon Ink Chemical Co., Ltd.)
-Thermal polymerization inhibitor N-nitrosophenylhydroxylamine 0.03 parts by mass Aluminum salt-Methyl ethyl ketone 58 parts by mass-Propylene glycol monomethyl ether acetate 53 parts by mass

(Formation of protective layer)
A mixed aqueous solution of polyvinyl alcohol (saponification degree: 98 mol%, polymerization degree: 500) and polyvinylpyrrolidone (BASF Corp., Rubiscor K-30) is applied to the surface of the photosensitive layer with a wire bar. The lithographic printing plate precursor was obtained by drying at 125 ° C. for 75 seconds in a drying apparatus. The content of polyvinyl alcohol / polyvinylpyrrolidone was 4/1% by mass, and the coating amount (coating amount after drying) was 2.45 g / m ² .

[Comparative Examples 1-4]
In Example 1, the average surface roughness (Ral) in the width direction of the back surface of the support obtained by changing the buffing conditions of the support was 0.16 μm, and the average surface roughness (Ras) in the longitudinal direction was 0.1. A laminate of a lithographic printing plate precursor was obtained in the same manner as in Examples 1, 6, 11, and 12, except that a 12 μm support was used.

Example 13
A lithographic printing plate precursor of Example 13 was obtained in the same manner as in Example 1 except that a back coat layer as shown below was formed on the back surface of the support described in Example 1.
(Formation of back coat layer)
The following backcoat layer forming coating solution [BC-1] was prepared and applied to the surface of the aluminum support used in Example 1 on the surface where the photosensitive layer was not formed, using a wire bar. Drying was performed at 100 ° C. for 70 seconds with a hot air drying apparatus to obtain a support on which a backcoat layer was formed. The total coating amount of this back coat layer (the coating amount after drying) was 0.46 g / m ² .

<Backcoat layer forming coating solution [BC-1]>
Novolak resin A: phenol / m-cresol / p-cresol = 5: 3: 2 (molar ratio), weight average molecular weight: 5,300 1.00 g
・ Fluorine surfactant 0.005g
(Megafuck F-780-F, Dainippon Ink and Chemicals,
Methyl isobutyl ketone (MIBK) 30% by mass solution)
・ Methyl ethyl ketone 22.5g
・ 2.5 g of 1-methoxy-2-propanol

[Examples 14 to 15]
In Example 13, instead of the novolak resin A used in the backcoat layer-forming coating solution [BC-1], in Example 14, pyrogallol resin (the following structure, weight average molecular weight: 3,000), Example 15 was used. In Example 13, except that a backcoat layer was formed using a backcoat layer-forming coating solution obtained by adding an equal amount of butyral resin (ESREC KS-10, Sekisui Chemical Co., Ltd.) to the novolak resin A, respectively. In the same manner, lithographic printing plate precursors of Example 14 and Example 15 were obtained.

[Comparative Example 5]
Example 13 except that a support having an average roughness (Ral) in the width direction of the back surface of the support after the anodic acid value treatment of 0.25 and an average roughness (Ras) in the longitudinal direction of 0.21 was used. Similarly, Comparative Example 5 was obtained.

[Evaluation]
(Average surface roughness (Ra))
The average roughness in the width direction (Ral) and the longitudinal direction (Ras) on the back surface of the support in each Example and Comparative Example was measured by “Surfcom” manufactured by Tokyo Seimitsu Co., Ltd.
(Scratch evaluation)
20 sheets of the obtained lithographic printing plate precursor were laminated without interposing a slip sheet therebetween to form a laminate. This laminated body is placed on the planographic printing plate precursor of the present invention that has already been set in the cassette, and is shifted from the edge by 5 cm (the stacked 20 plate materials protrude from the edge of the plate material in the cassette to the outside by 5 cm). ) After that, the edges of the 20 printing plates that were popped out were pushed in the horizontal direction, and the back surface Al of the 20 lowest stacked plates rubbed the surface of the uppermost printing plate in the cassette. Installed. The plate material rubbed on the surface of the protective layer with the back surface of the Al support was used as a plate material for evaluation of scratch resistance. It was conveyed from a setting part to a Trendsetter 3244 manufactured by Creo by an autoloader, and a 50% flat screen image was exposed at a resolution of 2400 dpi at an output of 7 W, an external drum rotational speed of 150 rpm, and a plate surface energy of 110 mJ / cm ² . After the exposure, development processing was performed in the same manner as the sensitivity evaluation. The presence or absence of scratches generated in the flat screen image of the obtained lithographic printing plate was visually evaluated. The number of scratches generated in 100 sheets was counted. As a result of this visual evaluation, a level having no practical problem was marked with ◯, and a practically impossible level was marked with ×.
The results are shown in Table 1.

From the results of Table 1, in the planographic printing plate precursors of Examples 1 to 12 having an average surface roughness Ra of 0.15 or less on the back surface of the support, scratches due to kosle occur on the opposing photosensitive material surface. In addition, the static friction coefficient is also an area that can be handled, and it is possible to operate without interposing the interleaf. On the other hand, it can be seen that the lithographic printing plates of Comparative Examples 1 to 4 with Ra greater than 0.15 cause scratches on the surface of the light-sensitive material and cause a practical problem.
Moreover, if the average surface roughness (Ra) in the longitudinal direction and the width direction of the back surface of the support is within the range of the present invention, the present lithographic printing plate precursors of Examples 13 to 15 having a back coat layer are also used. The excellent effect of the invention was obtained. However, as is apparent from Comparative Example 5, even when a backcoat layer is provided, the average surface roughness (Ra) in the longitudinal direction and the width direction of the back surface of the support is outside the scope of the present invention. It was inferior to.

1 is a perspective view of an embodiment of a lithographic printing plate precursor according to the present invention. FIG. 3 is a conceptual diagram used for explaining a longitudinal direction and a width direction of a lithographic printing plate precursor. It is a flowchart figure which shows an example of the manufacturing process of the lithographic printing plate precursor of this invention. It is a schematic diagram which shows an example of the anodizing apparatus used for the manufacturing process of the lithographic printing plate precursor of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 ... Planographic printing plate precursor 12 ... Support body 12 ... Surface 14 of support body ... Photosensitive layer 20 ... Anodizing apparatus 22 ... Feeding tank 24 ... Electrolytic processing tank 26 32 ... Electrolytic solution 28, 34 ... Electrode 30 ... Aluminum alloy plate 36 ... Conveying roller

Claims (10)

  A lithographic printing plate precursor in which a photosensitive layer sensitive to laser light is provided on the surface of a support, wherein the average surface roughness (Ra) in the longitudinal direction and the width direction of the back surface of the support are both 0. A lithographic printing plate precursor having a size of 15 μm or less.   2. The lithographic printing plate precursor as claimed in claim 1, wherein the average surface roughness (Ra) in the longitudinal direction and the width direction of the back surface of the support is 0.13 μm or less.   The lithographic printing plate precursor as claimed in claim 1 or 2, wherein the support comprises aluminum.   The lithographic printing plate precursor as claimed in any one of claims 1 to 3, wherein the Bekk smoothness of the surface sensitive to the laser beam of the lithographic printing plate precursor is 10,000 seconds or less.   The lithographic printing plate precursor as claimed in any one of claims 1 to 4, wherein the photosensitive layer contains a photosensitive polymerization initiator.   The lithographic printing plate precursor as claimed in any one of claims 1 to 5, further comprising a protective layer on the photosensitive layer.   The lithographic printing plate precursor as claimed in claim 6, wherein the protective layer has a filler.   The lithographic printing plate precursor as claimed in any one of claims 1 to 7, wherein the photosensitive layer contains an infrared absorbing dye having a maximum absorption wavelength between 750 nm and 1400 nm.   The lithographic printing plate precursor as claimed in claim 1, wherein the photosensitive layer contains a sensitizing dye having a maximum absorption wavelength between 350 nm and 450 nm.   Lamination of a lithographic printing plate precursor, wherein the uppermost layer of the lithographic printing plate precursor according to any one of claims 1 to 9 is laminated in direct contact with the back surface of the support. body.

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