JP2012071557A - Lithographic printing plate precursor, lithographic printing method, and organic clay composite - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a lithographic printing pate precursor that can efficiently form images using laser exposure without having coagulation precipitation in a protective layer coating liquid although a protective layer includes an inorganic layer compound, and is excellent in plate wear, receptivity and on-press development, and to provide a lithographic printing method using the lithographic printing plate precursor.SOLUTION: The lithographic printing plate precursor includes, on a support: an image recording layer including a polymeric initiator and a radically polymerizable compound; and the protective layer including the inorganic laminar compound. Also the lithographic printing plate precursor includes a specific functional group having ammonium or phosphonium, and a polymer having specific (meth)acrylamide unit in at least the image recording layer or the protective layer.

Description

  The present invention relates to a lithographic printing plate precursor and a lithographic printing method using the same. More specifically, the present invention relates to a lithographic printing plate precursor that can be directly made by laser image exposure and a plate making method (printing method) for developing the lithographic printing plate precursor on-press. The present invention also relates to an organoclay complex necessary for producing the lithographic printing plate precursor.

In general, a lithographic printing plate comprises an oleophilic image area that receives ink in the printing process and a hydrophilic non-image area that receives dampening water. Lithographic printing utilizes the property that water and oil-based inks repel each other, so that the oleophilic image area of the lithographic printing plate is the ink receiving area, and the hydrophilic non-image area is dampened with the water receiving area (ink non-receiving area). In this method, a difference in ink adhesion is caused on the surface of the lithographic printing plate, and after ink is applied only to the image area, the ink is transferred to a printing medium such as paper and printed.
In order to produce this lithographic printing plate, conventionally, a lithographic printing plate precursor (PS plate) in which an oleophilic photosensitive resin layer (image recording layer) is provided on a hydrophilic support is used. After exposure through a mask such as a film, development with an alkaline developer is performed to leave the image recording layer corresponding to the image area, and dissolve and remove the unnecessary image recording layer corresponding to the non-image area. And obtained a lithographic printing plate.

  Due to recent advances in this field, lithographic printing plates are now available with CTP (computer to plate) technology. That is, a lithographic printing plate can be obtained by scanning and exposing a lithographic printing plate precursor directly using a laser or a laser diode without a lith film, and developing it.

  Along with the above progress, problems related to the lithographic printing plate precursor have been changed to improvements in image formation characteristics, printing characteristics, physical characteristics and the like corresponding to the CTP technology. In addition, due to increasing interest in the global environment, environmental issues related to waste liquids associated with wet processing such as development processing have been highlighted as another issue related to lithographic printing plate precursors.

For the above environmental problems, simplification and no processing of development or plate making are directed. As one simple plate making method, a method called “on-press development” is performed. That is, after the exposure of the lithographic printing plate precursor, conventional development is not performed, but it is mounted on a printing machine as it is, and unnecessary portions of the image recording layer are removed at the initial stage of a normal printing process.
In addition, as a simple development method, a method called “gum development” in which unnecessary portions of the image recording layer are removed with a finisher or gum solution having a pH close to neutral instead of a conventional highly alkaline developer is also performed. ing.

  In the simplification of the plate making operation as described above, a system using a lithographic printing plate precursor and a light source that can be handled in a bright room or under a yellow light is preferable in terms of ease of work. A solid-state laser such as a semiconductor laser or a YAG laser emitting an infrared ray of 1200 nm is used. Further, a UV laser can be used.

  As a lithographic printing plate precursor capable of on-machine development, for example, in Patent Documents 1 and 2, a lithographic printing plate having an image recording layer (thermosensitive layer) containing a microcapsule containing a polymerizable compound on a hydrophilic support. The original edition is listed. Patent Document 3 describes a lithographic printing plate precursor in which an image recording layer (photosensitive layer) containing an infrared absorber, a radical polymerization initiator, and a polymerizable compound is provided on a support. Further, in Patent Document 4, on-press development is possible in which an image recording layer containing a polymerizable compound and a graft polymer having a polyethylene oxide chain in the side chain or a block polymer having a polyethylene oxide block is provided on a support. A planographic printing plate precursor is described.

  In Patent Document 5, in order to improve on-press developability, fine line reproducibility, printing durability and on-press development running property of an on-press developable lithographic printing plate, a specific inorganic layered compound is included in the overcoat layer. It is described to contain. These lithographic printing plates were not sufficiently satisfactory in ink adhesion (thickness) during printing.

  Patent Document 6 describes a lithographic printing plate precursor having a protective layer containing an inorganic layered compound modified with an organic cation. Although these lithographic printing plate precursors exhibit sufficient thickness at the time of printing, when preparing the lithographic printing plate precursor, the inorganic layered compound aggregates and settles over time in the coating solution for forming the protective layer. There was something to do.

  Patent Document 7 describes a lithographic printing plate precursor containing a layered compound in a protective layer and containing a polymer containing a structural unit having an ammonium structure as a repeating unit in at least one of the image recording layer and the protective layer. ing. Although these lithographic printing plate precursors exhibit sufficient ink adhesion at the time of printing, examples in which a polymer containing a structural unit having an ammonium structure as a repeating unit is added to the protective layer when a lithographic printing plate precursor is prepared are described. Absent.

  Patent Document 8 describes an organoclay complex in which quaternary ammonium ions are introduced between layers of a swellable layered silicate.

JP 2001-277740 A JP 2001-277742 A JP 2002-287334 A US Patent Application Publication No. 2003/0064318 JP 2005-119273 A JP 2006-297907 A JP 2009-208458 A JP-A-6-287014

  The object of the present invention is that there is no aggregation and precipitation of the inorganic layered compound in the protective layer coating solution, the layered compound is contained in the protective layer, an image can be formed efficiently by laser exposure, and the printing durability is improved. An object of the present invention is to provide a lithographic printing plate precursor having excellent inking properties and on-press developability, and a lithographic printing method using the same. Another object of the present invention is to provide an organoclay composite used in the lithographic printing plate precursor.

As a result of intensive investigations to achieve the above object, the present inventors have used a specific compound having a specific cationic group and a specific structural unit, thereby producing a lithographic printing plate precursor in a protective layer coating solution. The present inventors have found that a lithographic printing plate precursor excellent in all of the storage stability, printing durability, inking property and on-press development property can be obtained.
That is, the present invention is as follows.

1. A lithographic printing plate precursor having, on a support, an image recording layer containing a polymerization initiator and a radical polymerizable compound, and a protective layer containing an inorganic layered compound, the functional group represented by the following general formula (1) And a polymer having a structural unit represented by the following general formula (2) in at least one of the image recording layer and the protective layer.

In the formula, R _{1 to} R ₃ each independently represents an alkyl group or an aryl group having 1 to 7 carbon atoms, and any two of R _{1 to} R ₃ may form a ring, and X is N or P represents L ₁ represents a divalent linking group, Y ⁻ represents a counter anion, R ₄ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R _{5 to} R ₆ each independently Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, or R ₅ and R ₆ are connected to each other to represent —CH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ CH ₂ —, —CH ₂ CH _2. CH ₂ CH ₂ CH ₂ — or —CH ₂ CH ₂ OCH ₂ CH ₂ — is represented.

2. 2. The lithographic printing plate precursor as described in 1 above, wherein the image recording layer contains a polymer having a functional group represented by the general formula (1) and a structural unit represented by the general formula (2).
3. 2. The lithographic printing plate precursor as described in 1 above, wherein the protective layer contains a polymer having a functional group represented by the general formula (1) and a structural unit represented by the general formula (2).
4). After replacing the cation present in the inorganic layered compound with a polymer having a functional group represented by the general formula (1) and a structural unit represented by the general formula (2) to form an organoclay complex, coating with a protective layer 4. The lithographic printing plate precursor as described in 3 above, wherein a protective layer is formed by adding to a liquid and coating on the image recording layer.
5. 5. The lithographic printing plate precursor as described in any one of 1 to 4 above, wherein the functional group represented by the general formula (1) is present at the end of the main chain of the polymer.
6). In the general formula (1), R ₁ and R ₂ are each independently selected from a methyl group, an ethyl group, a propyl group, a butyl group and a phenyl group, and R ₃ is a methyl group, an ethyl group, a propyl group, a butyl group, a benzyl group The lithographic printing plate precursor as described in any one of 1 to 5 above, which is selected from a group and a phenyl group.
7). In the general formula (2), R ₄ is selected from a hydrogen atom and a methyl group, and R ₅ and R ₆ are each independently selected from a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, and a tert-butyl group. Or the lithographic printing according to any one of 1 to 6 above, wherein R ₅ and R ₆ are connected to form —CH ₂ CH ₂ OCH ₂ CH ₂ —. Version original edition.
8). The lithographic printing plate precursor as described in any one of 1 to 7 above, wherein the inorganic layered compound is at least one selected from smectite and mica.
9. The lithographic printing according to 1 or 3 above, wherein the protective layer further contains a water-soluble polymer other than the polymer having the functional group represented by the general formula (1) and the structural unit represented by the general formula (2). Version original edition.
10. 3. The lithographic printing plate as described in 1 or 2 above, wherein the image recording layer further contains a polymer other than the polymer having the functional group represented by the general formula (1) and the structural unit represented by the general formula (2). Original edition.
11. 2. The lithographic printing plate precursor as described in 1 above, wherein the image recording layer further contains an infrared absorber.
12 The lithographic printing plate precursor according to any one of 1 to 11 above is imagewise exposed with a laser, and then mounted on a printing machine and developed by supplying at least one of ink and fountain solution, and printing A lithographic printing method comprising:

13. An organoclay composite obtained by replacing a cation present in an inorganic layered compound with a polymer having a functional group represented by the general formula (1) and a structural unit represented by the general formula (2).
14 14. The organoclay composite as described in 13 above, wherein the functional group represented by the general formula (1) is present at the end of the main chain of the polymer.
15. In the general formula (1), R ₁ and R ₂ are each independently selected from a methyl group, an ethyl group, a propyl group, a butyl group and a phenyl group, and R ₃ is a methyl group, an ethyl group, a propyl group, a butyl group, 15. The organoclay complex as described in 13 or 14 above, which is selected from a benzyl group and a phenyl group.
16. In the general formula (2), R ₄ is selected from a hydrogen atom and a methyl group, and R ₅ and R ₆ are each independently selected from a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, and a tert-butyl group. Any one of the above 13 to 15, wherein R ₅ and R ₆ are linked together to form —CH ₂ CH ₂ OCH ₂ CH ₂ —. The organoclay complex described in 1.
17. 17. The organoclay composite according to any one of 13 to 16, wherein the inorganic layered compound is at least one selected from smectite and mica.

  According to the present invention, there is no aggregation and sedimentation of the inorganic layered compound in the protective layer coating solution for preparing a lithographic printing plate precursor, an image can be formed efficiently by laser exposure, and excellent in printing durability. A lithographic printing plate precursor having excellent inking properties and on-press developability, and a lithographic printing method using the same.

It is explanatory drawing which shows the structure of an automatic developing processor.

[Lithographic printing plate precursor]
The lithographic printing plate precursor of the present invention is a lithographic printing plate precursor having an image recording layer containing a polymerization initiator and a radically polymerizable compound on a support and a protective layer containing an inorganic layered compound in this order, A polymer having a cationic group and a specific structural unit (hereinafter abbreviated as a specific compound) is contained in the image recording layer and / or the protective layer. Hereinafter, the present invention will be described in detail.

<Specific compounds>
The specific compound used in the present invention is a polymer having a functional group represented by the following general formula (1) and a structural unit represented by the following general formula (2), and has a mass average molar mass (Mw) of 500 or more and 50000. The following polymers are preferred.

In the formula, R _{1 to} R ₃ each independently represents an alkyl group or an aryl group having 1 to 7 carbon atoms, and any two may form a ring, X represents N or P, and L ₁ Represents a divalent linking group, Y ⁻ represents a counter anion, R ₄ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R _{5 to} R ₆ each independently represents a hydrogen atom or a carbon atom number. Represents an alkyl group of 1 to 4, or R ₅ and R ₆ are connected to each other to represent —CH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ CH ₂ CH _2. - or _{-CH 2 CH 2 OCH 2 CH 2} - represents a.

Specific examples of the alkyl group having 1 to 7 carbon atoms represented by R _{1 to} R ₃ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, isobutyl. Group, pentyl group, hexyl group, heptyl group, benzyl group and the like. Specific examples of the aryl group include a phenyl group and a tolyl group. Among these, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, a benzyl group, and a phenyl group are preferable. _As the combination of _{R 1, R 2, R 3} , and more preferably combinations shown below.
(R ₁ , R ₂ , R ₃ ) = (methyl group, methyl group, methyl group), (methyl group, methyl group, ethyl group), (methyl group, methyl group, propyl group), (methyl group, methyl group) , Butyl group), (ethyl group, ethyl group, ethyl group), (butyl group, butyl group, butyl group), (phenyl group, phenyl group, phenyl group).

X may be either N or P, but N is particularly preferred from the availability of raw materials.
The divalent linking group represented by L ₁ includes 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 100 carbon atoms. It is preferably composed of hydrogen atoms and 0 to 20 sulfur atoms.
More specifically, the following divalent groups or groups formed by appropriately combining these groups can be exemplified.

Counter anions represented by Y ⁻ include halide anions such as Cl ⁻ , Br ⁻ and I ⁻ , nitrate anions, sulfate anions, hydrogen sulfate anions, monoester sulfate anions such as monomethyl sulfate and monoethyl sulfate, phosphate anions , Hydrogen phosphate anion, phosphate dihydrogen anion, phosphate monoester anion such as monomethyl phosphate, phosphate diester anion such as dimethyl phosphate, hexafluorophosphate anion, tetrafluoroborate anion, p-toluenesulfonic acid And sulfonic acid anions such as methanesulfonic acid and trifluoromethanesulfonic acid, and carboxylic acid anions such as acetic acid, benzoic acid, and trifluoroacetic acid. Of these, halide anions, sulfuric monoester anions, and sulfonate anions are particularly preferred.

The functional group represented by the general formula (1) is present at the end of the main chain or the side chain in the polymer, but is particularly preferably present at the end of the main chain.
The functional group represented by the general formula (1) is preferably present in the polymer at 0.01 mmol / g or more and 10 mmol / g or less, particularly preferably 0.02 mmol / g or more and 5 mmol / g or less. preferable. Within this range, good coating solution stability and wearability can be obtained.

Specific examples of the alkyl group having 1 to 4 carbon atoms represented by R _{4 to} R ₆ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, and isobutyl. Groups. R ₄ is preferably a hydrogen atom or a methyl group. R ₅ and R ₆ are preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, or —CH ₂ CH ₂ OCH ₂ CH ₂ — in which R ₅ and R ₆ are linked. As combinations of R ₅ and R _6, the combinations shown below are preferable.
(R ₅ , R ₆ ) = (hydrogen atom, hydrogen atom), (hydrogen atom, methyl group), (hydrogen atom, ethyl group), (hydrogen atom, isopropyl group), (hydrogen atom, propyl group), (methyl Group, methyl group), (ethyl group, ethyl group), (—CH ₂ CH ₂ OCH ₂ CH ₂ — in which R ₅ and R ₆ are linked)

The structural unit represented by the general formula (2) is preferably 30 mol% or more and 100 mol% or less, and 40 mol% or more and 100 mol% or less, assuming that the structural unit forming the specific compound is 100 mol%. More preferably, it is 50 mol% or more and 100 mol% or less. Within this range, good coating solution stability and wearability can be obtained.
Two or more kinds of structural units represented by the general formula (2) may be contained in the specific compound.

  The specific compound used in the present invention may have a structural unit represented by the following general formula (3) in addition to the structural unit represented by the general formula (2).

In the formula, R ₇ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L ₂ represents a divalent linking group, and R ₈ represents an alkyl group or aryl group having 1 to 18 carbon atoms.
Specific examples of the alkyl group having 1 to 4 carbon atoms represented by R ₇ include the alkyl group represented by R ₄ . R ₇ is preferably a hydrogen atom or a methyl group.
Specific examples of the divalent linking group represented by L ₂ include a single bond and the linking group represented by L ₁ . L ₂ is preferably a linking group or a single bond shown below.

In the formula, * represents a linking position for C and R _{8 in the} structural unit represented by the general formula (3), and R ₉ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an aryl group.

Specific examples of the alkyl group having 1 to 18 carbon atoms and aryl group represented by R ₈ and R ₉ include alkyl group and octyl group, nonyl group, decyl group, dodecyl group, octadecyl group, phenyl represented by R _1. Group, cyclohexyl group, cyclopentyl group, isobornyl group, adamantyl group, naphthyl group, 2-ethylhexyl group, 2-hydroxyethyl group, 2-methoxyethyl group, 2- (2-methoxyethoxy) ethyl group, 4-tert-butyl A phenyl group etc. are mentioned. Among these, as R ₈ , methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, 2-ethylhexyl group, pentyl group, hexyl group, cyclohexyl group, benzyl group, phenyl group , Isobornyl group, dodecyl group and octadecyl group are preferable, and R ₉ is preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group or an isobutyl group.

The structural unit represented by the general formula (3) is preferably 0 mol% or more and 70 mol% or less, and 0 mol% or more and 60 mol% or less, assuming that the structural unit forming the specific compound is 100 mol%. It is more preferable that it is 0 mol% or more and 50 mol% or less. Within this range, good coating solution stability and wearability can be obtained.
Two or more types of structural units represented by the general formula (3) may be contained in the specific compound.

  Specific examples of the specific compound used in the present invention are shown below. The present invention is not limited to these. In addition, P-1-P-17 show each synthesis example and Mw in an Example.

  The mass average molar mass (gel permeation chromatography (GPC) / polystyrene equivalent value) of the specific compound used in the present invention is preferably 500 or more and 50000 or less, more preferably 700 or more and 40000 or less, and particularly preferably 900 or more and 30000 or less.

The specific compound used in the present invention is contained in the image recording layer and / or the protective layer, but is particularly preferably contained in the protective layer. When contained in the protective layer, the inorganic layered compound described below and the specific compound may be mixed at the time of preparing the protective layer coating solution, and the cation contained in the inorganic layered compound is replaced with the specific compound to form an organic layer. A clay complex may be formed, and the organoclay complex may be mixed at the time of preparing the protective layer coating solution, but it is particularly preferable to mix after forming the organoclay complex. By containing it in the protective layer, ink fillability, printing durability and developability are improved. The same effect can be obtained even if a specific compound is contained in the image recording layer. This is presumed that the specific compound in the image recording layer moved to the protective layer when the protective layer coating solution was applied or after the coating, thereby forming an organic composite.
When contained in the image recording layer, the content is preferably 0.01 to 30% by mass, more preferably 0.1 to 15% by mass, when the total solid content of the image recording layer is 100% by mass. 1-10 mass% is especially preferable. When the specific compound is contained in the protective layer, the content is preferably from 5 to 98 mass%, more preferably from 10 to 95 mass%, more preferably from 15 to 90 mass% when the total solid content of the protective layer is 100 mass%. Mass% is particularly preferred.

[Protective layer]
The protective layer used in the lithographic printing plate precursor according to the invention contains an inorganic layered compound as an essential component. The inorganic layered compound is added to the protective layer as it is, or is added as an organic clay complex that is cation-substituted with a specific compound. Moreover, you may contain a polymer, a plasticizer, surfactant, an inorganic fine particle, etc. as another arbitrary component. Hereinafter, each component will be described.

<Inorganic layered compound>
The inorganic layered compound used in the present invention is an inorganic layered compound having a cation exchange ability, which is a particle having a thin flat plate shape, and examples thereof include smectite, vermiculite, and mica. Of these, smectite and mica are preferable.

As the smectite, for example, natural or chemically synthesized materials such as hectorite, saponite, stevensite, beidellite, montmorillonite, nontronite, bentonite, etc., or substituted products, derivatives thereof, or mixtures thereof can be exemplified. .
Examples of the mica include natural mica such as muscovite, soda mica, phlogopite, biotite, and mica, fluorine phlogopite KMg ₃ (AlSi ₃ O ₁₀ ) F ₂ , potash tetrasilicon mica KMg _2.5 Si ₄ O ₁₀₎ non-swellable mica ₂ such _F, and Na tetrasilylic 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 And synthetic mica such as swellable mica such as montmorillonite-based Na or Li hectorite (Na, Li) _1/8 Mg _2/5 Li _1/8 (Si ₄ O ₁₀ ) F ₂ .
Among these layered compounds, fluorine-based swellable mica which is a synthetic layered compound is particularly useful.

Swelling clay minerals such as mica, montmorillonite, saponite, hectorite, bentonite, etc. have a laminated structure composed of unit crystal lattice layers with a thickness of about 10 to 15 mm, and the substitution of metal atoms in the lattice is another viscosity mineral It is significantly larger. As a result, the lattice layer suffers from a shortage of positive charge, and in order to compensate for this, the layers such as Li ⁺ , Na ⁺ , Ca ²⁺ , Mg ²⁺ , amine salts, quaternary ammonium salts, phosphonium salts and sulfonium salts Adsorbs organic cation cations. These layered compounds swell with water. If shear is applied in this state, it will easily cleave and form a stable sol in water. Bentonite and swelling synthetic mica have this tendency.

  As the shape of the layered compound, from the viewpoint of diffusion control, the thinner the better, the better the planar size 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, for example, from a projected view of the particle by a micrograph. The larger the aspect ratio, the greater the effect that can be obtained.

  As for the particle diameter of the layered compound, the average major axis is 0.3 to 20 μm, preferably 0.5 to 10 μm, particularly preferably 1 to 5 μm. A particle diameter of 0.3 μm or more is preferable because the suppression of permeation of oxygen and moisture can be further improved and the effect can be further exhibited. Moreover, if it is 20 micrometers or less, since the dispersion stability in a coating liquid improves more and can apply | coat more stably, it is preferable. The average thickness of the particles is 0.1 μm or less, preferably 0.05 μm or less, particularly preferably 0.01 μm or less. For example, among inorganic layered compounds, the size of the swellable synthetic mica that is a representative compound is about 1 to 50 nm in thickness and about 1 to 20 μm in surface size.

<Organic clay complex>
The organoclay complex used in the lithographic printing plate precursor according to the invention is an organoclay complex obtained by substituting the cation of the inorganic layered compound with a specific compound.
When the inorganic layered compound used for producing the organoclay composite of the present invention is a swellable layered silicate, the cation exchange capacity is 10 milliequivalents or more, preferably 60 milliequivalents or more per 100 g of clay. In the case of synthetic smectite, it is 85 to 130 milliequivalents, and the larger the exchange capacity, the better. The swellable layered silicate may contain 50% by mass or less of non-clay impurities, but the amount of non-clay impurities is preferably 10% by mass or less.

  The organoclay composite of the present invention is obtained by cation exchange between layers, and can be produced, for example, by the following method. In the first step, the inorganic stratiform compound is dispersed in water, and the solid dispersion concentration is usually preferably 1 to 15% by mass, but can be freely set as long as the concentration of the inorganic stratiform compound is sufficiently dispersible. . In this case, using an inorganic layered compound that has been freeze-dried in advance is effective for easily producing an organoclay composite. In the second step, the above-mentioned specific compound solution is added to this inorganic layered compound suspension, or conversely, the organic clay complex is also produced by adding the inorganic layered compound suspension to the above-mentioned specific compound solution. Is possible.

  The specific compound is preferably added in an amount equivalent to the cation exchange capacity of the inorganic layered compound as the functional group represented by the general formula (1), but can be produced even in an amount smaller than this. Moreover, there is no problem even if an excessive amount is added to the cation exchange capacity. The amount is preferably 0.5 to 1.5 times (milli equivalent equivalent), particularly 0.8 to 1.4 times the cation exchange capacity of the inorganic layered compound.

  The reaction proceeds sufficiently at room temperature, but may be warmed. The maximum temperature of the heating is governed by the heat resistance of the specific compound used, and can be arbitrarily set as long as it is below the decomposition point, but it is preferably carried out in the range of room temperature to 80 ° C. Next, the suspension is centrifuged as necessary to separate the solid and the liquid, and the produced organic clay complex is washed with water to sufficiently remove the by-product electrolyte. This is dried and pulverized as necessary to obtain a final product. In order to make cation exchange more complete, after the solid and the liquid are separated, a solution of the specific compound may be further added to perform the same reaction, separation, purification, and drying.

  The formation of the organoclay complex of the present invention can be easily confirmed by measuring the position of (001) bottom reflection, for example, by X-ray diffraction. Synthetic smectite as a raw material has a bottom surface interval of 10 to 15% in a dehydrated state and 12 to 15 tons under normal temperature and humidity, but the organoclay complex of the present invention is 15 to more than 15Å depending on the structure of the specific compound. From this, it can be seen that an organoclay complex is formed. Moreover, it can heat easily more than the decomposition temperature of a specific compound by thermogravimetric analysis (TGA), and can confirm easily also by the weight reduction rate.

  Next, an example of a general dispersion method when a layered compound is used for the protective layer will be described. First, 5 to 10 parts by mass of the above-mentioned inorganic layered compound or organoclay complex is added to 100 parts by mass of water, and the mixture is thoroughly blended with water and swollen, and then dispersed using a disperser. Examples of the disperser used here include various mills that disperse mechanically by applying a direct force, a high-speed stirring disperser having a large shearing force, and a disperser that provides high-intensity ultrasonic energy. Specifically, ball mill, sand grinder mill, visco mill, colloid mill, homogenizer, tisol bar, polytron, homomixer, homo blender, ketdy mill, jet agitator, capillary emulsifier, liquid siren, electrostrictive ultrasonic generator, An emulsifying device having a Paulman whistle can be used. The dispersion of 5 to 10% by mass of the inorganic layered compound or organoclay complex dispersed by the above method is highly viscous or gelled, and the storage stability is very good. When preparing a protective layer coating solution using this dispersion, it is preferably prepared by diluting with water and stirring sufficiently, and then optionally blending with a solution containing other components.

  The content of the inorganic stratiform compound in the protective layer is preferably 1% by mass or more and 95% by mass or less, and preferably 2% by mass or more and 90% by mass or less with respect to the total solid content used in the protective layer. More preferably, the content is 3% by mass or more and 85% by mass or less. Even when a plurality of types of inorganic layered compounds are used in combination, the total amount of these inorganic layered compounds is preferably within the above range.

<Other ingredients>
In the lithographic printing plate precursor according to the invention, the protective layer may contain a polymer as an optional component other than the above compounds. As such a polymer, either a water-soluble polymer or a water-insoluble polymer can be appropriately selected and used, and two or more kinds can be mixed and used as necessary. Specifically, for example, polyvinyl alcohol, modified polyvinyl alcohol, polyvinyl pyrrolidone, water-soluble cellulose derivative, poly (meth) acrylonitrile, polyacrylamide, poly N-isopropylacrylamide, polydimethylacrylamide, acrylamide-acrylic acid ester copolymer, etc. Is mentioned.
As the modified polyvinyl alcohol, acid-modified polyvinyl alcohol having a carboxylic acid group or a sulfonic acid group is preferably used. Specifically, modified polyvinyl alcohols described in JP-A-2005-250216 and JP-A-2006-259137 are preferable.
Further, the protective layer may contain known additives such as a plasticizer for imparting flexibility, a surfactant for improving coating properties, and inorganic fine particles for controlling surface slipperiness.

The protective layer is applied by a known method. The coating amount of the protective layer, the coating amount after drying is preferably in the range of 0.01 to 10 g / ^{m 2,} more preferably in the range of 0.02 to 3 g / ^{m 2,} and most preferably 0. in the range of 02~1g / ^{m 2.}

(Image recording layer)
In the lithographic printing plate precursor according to the invention, the image recording layer contains a polymerization initiator and a radical polymerizable compound as compounds for forming a printed image.

<Polymerization initiator>
The polymerization initiator used in the present invention is a compound that initiates and accelerates the polymerization of a radical polymerizable compound. As the polymerization initiator that can be used in the present invention, a radical polymerization initiator is preferable, and a known thermal polymerization initiator, a compound having a bond with a small bond dissociation energy, a photopolymerization initiator, and the like can be used. Among these, a photopolymerization initiator is preferable.
Examples of the radical polymerization initiator in the present invention include (a) an organic halide, (b) a carbonyl compound, (c) an azo compound, (d) an organic peroxide, (e) a metallocene compound, and (f) an azide compound. (G) hexaarylbiimidazole compound, (h) organic borate compound, (i) disulfone compound, (j) oxime ester compound, (k) onium salt compound.

(A) As the organic halide, compounds described in paragraph numbers [0022] to [0023] of JP-A-2008-195018 are preferable.
(B) As the carbonyl compound, compounds described in paragraph [0024] of JP-A-2008-195018 are preferable.
(C) As the azo compound, for example, an azo compound described in JP-A-8-108621 can be used.
(D) As the organic peroxide, for example, compounds described in paragraph [0025] of JP-A-2008-195018 are preferable.
As the (e) metallocene compound, for example, the compound described in paragraph [0026] of JP-A-2008-195018 is preferable.

(F) Examples of the azide compound include 2,6-bis (4-azidobenzylidene) -4-methylcyclohexanone.
(G) As the hexaarylbiimidazole compound, for example, a compound described in paragraph [0027] of JP-A-2008-195018 is preferable.
(H) As the organic borate compound, for example, a compound described in paragraph [0028] of JP-A-2008-195018 is preferable.
(I) Examples of the disulfone compound include compounds described in JP-A No. 61-166544.
(J) As the oxime ester compound, for example, compounds described in paragraph numbers [0028] to [0030] of JP-A-2008-195018 are preferable.

  (K) Examples of the onium salt compounds include S.I. I. Schlesinger, Photogr. Sci. Eng. 18, 387 (1974), T .; S. Bal et al, Polymer, 21, 423 (1980), diazonium salts described in JP-A-5-158230, ammonium described in US Pat. No. 4,069,055, JP-A-4-365049, and the like. Salt, phosphonium salts described in U.S. Pat. Nos. 4,069,055 and 4,069,056, EP 104,143, U.S. Patent Application Publication No. 2008/0311520 JP-A-2-150848, JP-A-2008-195018, or J.P. V. Ivonium salt described in Crivello et al, Macromolecules, 10 (6), 1307 (1977), European Patents 370,693, 233,567, 297,443, 297,442, US Patent 4,933,377, 4,760,013, 4,734,444, 2,833,827, German Patent 2,904,626, 3,604,580 Sulphonium salts described in the respective specifications of U.S. Pat. V. Crivello et al, J.A. Polymer Sci. , Polymer Chem. Ed. , 17, 1047 (1979), a selenonium salt described in C.I. S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), and onium salts such as azinium salts described in JP-A-2008-195018.

  Among these, more preferred are hexaarylbiimidazole compounds and onium salts, and among onium salts, iodonium salts, sulfonium salts and azinium salts are preferred. Specific examples of these compounds are shown below, but are not limited thereto.

  Examples of hexaarylbiimidazole compounds include 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-bromophenyl)- 4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o, p-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis (O-chlorophenyl) -4,4 ', 5,5'-tetra (m-methoxyphenyl) biimidazole, 2,2'-bis (o, o'-dichlorophenyl) -4,4', 5,5 ' -Tetraphenylbiimidazole, 2,2'-bis (o-nitrophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-methylphenyl) -4,4 ', 5,5'-te La biimidazole, 2,2'-bis (o-trifluoromethylphenyl) -4,4 ', 5,5'-tetraphenyl biimidazole. The hexaarylbiimidazole compound is particularly preferably used in combination with a sensitizing dye having a maximum absorption in a wavelength region of 300 to 450 nm.

  As an example of the iodonium salt, a diphenyl iodonium salt is preferable, and a diphenyl iodonium salt substituted with an electron donating group such as an alkyl group or an alkoxyl group is particularly preferable, and an asymmetric diphenyl iodonium salt is more preferable. Specific examples include diphenyliodonium = hexafluorophosphate, 4-methoxyphenyl-4- (2-methylpropyl) phenyliodonium = hexafluorophosphate, 4- (2-methylpropyl) phenyl-p-tolyliodonium = hexa. Fluorophosphate, 4-hexyloxyphenyl-2,4,6-trimethoxyphenyliodonium = hexafluorophosphate, 4-hexyloxyphenyl-2,4-diethoxyphenyliodonium = tetrafluoroborate, 4-octyloxy Phenyl-2,4,6-trimethoxyphenyliodonium = 1-perfluorobutanesulfonate, 4-octyloxyphenyl-2,4,6-trimethoxyphenyliodonium = hexafluorophosphate, bis ( -t- butylphenyl) iodonium tetraphenylborate and the like.

  Examples of sulfonium salts include triphenylsulfonium = hexafluorophosphate, triphenylsulfonium = benzoylformate, bis (4-chlorophenyl) phenylsulfonium = benzoylformate, bis (4-chlorophenyl) -4-methylphenylsulfonium = Examples thereof include tetrafluoroborate, tris (4-chlorophenyl) sulfonium = 3,5-bis (methoxycarbonyl) benzenesulfonate, and tris (4-chlorophenyl) sulfonium = hexafluorophosphate.

  Examples of azinium salts include 1-cyclohexylmethyloxypyridinium = hexafluorophosphate, 1-cyclohexyloxy-4-phenylpyridinium = hexafluorophosphate, 1-ethoxy-4-phenylpyridinium = hexafluorophosphate, 1-cyclohexyl (2-ethylhexyloxy) -4-phenylpyridinium = hexafluorophosphate, 4-chloro-1-cyclohexylmethyloxypyridinium = hexafluorophosphate, 1-ethoxy-4-cyanopyridinium = hexafluorophosphate, 3,4 -Dichloro-1- (2-ethylhexyloxy) pyridinium = hexafluorophosphate, 1-benzyloxy-4-phenylpyridinium = hexafluorophosphate, 1-phenethylo Ci-4-phenylpyridinium = hexafluorophosphate, 1- (2-ethylhexyloxy) -4-phenylpyridinium = p-toluenesulfonate, 1- (2-ethylhexyloxy) -4-phenylpyridinium = perfluorobutanesulfonate 1- (2-ethylhexyloxy) -4-phenylpyridinium bromide, 1- (2-ethylhexyloxy) -4-phenylpyridinium tetrafluoroborate.

  The onium salt is particularly preferably used in combination with an infrared absorber having a maximum absorption in a wavelength range of 750 to 1400 nm.

  The polymerization initiator is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and particularly preferably 0.8 to 20% by mass with respect to the total solid content constituting the image recording layer. Can be added. Within this range, good sensitivity and good stain resistance of the non-image area during printing can be obtained.

<Radically polymerizable compound>
The radical polymerizable compound used for the image recording layer in the present invention is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and has at least one, preferably two or more terminal ethylenically unsaturated bonds. Selected from compounds. These have chemical forms such as monomers, prepolymers, ie dimers, trimers and oligomers, or mixtures thereof. Examples of monomers include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters and amides thereof, preferably unsaturated carboxylic acids. An ester of an acid and a polyhydric alcohol compound and an amide of an unsaturated carboxylic acid and a polyvalent amine compound are used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxy group, an amino group or a mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and a monofunctional or polyfunctional compound. 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 In addition, a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. 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. These are disclosed in JP-T-2006-508380, JP-A-2002-287344, JP-A-2008-256850, JP-A-2001-342222, JP-A-9-179296, JP-A-9-179297. JP-A-9-179298, JP-A-2004-294935, JP-A-2006-243493, JP-A-2002-275129, JP-A-2003-64130, JP-A-2003-280187, It is described in references including Kaihei 10-333321.

  Specific examples of the monomer of the ester of a polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, Examples include trimethylolpropane triacrylate, hexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol tetraacrylate, sorbitol triacrylate, isocyanuric acid ethylene oxide (EO) -modified triacrylate, and polyester acrylate oligomer. Methacrylic acid esters include tetramethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, pentaerythritol trimethacrylate, bis [p- (3-methacryloxy-2-hydroxypropoxy) phenyl ] Dimethylmethane, bis- [p- (methacryloxyethoxy) phenyl] dimethylmethane, and the like. Specific examples of amide monomers of polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis-methacrylic. Examples include amide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, and xylylene bismethacrylamide.

  In addition, urethane-based addition-polymerizable compounds produced by using an addition reaction between an isocyanate and a hydroxy group are also suitable, and specific examples thereof include, for example, one molecule described in Japanese Patent Publication No. 48-41708. A vinyl containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxy group represented by the following general formula (A) to a polyisocyanate compound having two or more isocyanate groups. A urethane compound etc. are mentioned.

^{_{CH 2 = C (R 4)}} COOCH 2 CH (R 5) OH (A)
(However, R ⁴ and R ⁵ represent H or CH _3. )

  Also, urethanes described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-A-2003-344997, and JP-A-2006-65210. Acrylates, JP-B 58-49860, JP-B 56-17654, JP-B 62-39417, JP-B 62-39418, JP-A 2000-250211, JP-A 2007-94138 Urethane compounds having an ethylene oxide-based skeleton described in the publication, and urethane compounds having a hydrophilic group described in US Pat. No. 7,153,632, JP-T 8-505958, JP-A 2007-293221, and JP-A 2007-293223. Are also suitable.

  Among them, tris (acryloyloxyethyl) isocyanurate, bis (acryloyloxyethyl) hydroxyethyl isocyanurate, etc. are excellent in the balance between the hydrophilicity involved in on-press developability and the polymerization ability involved in printing durability. Isocyanuric acid ethylene oxide modified acrylates are particularly preferred.

  Details of the usage method such as the structure of these polymerizable compounds, whether they are used alone or in combination, and the amount added can be arbitrarily set in accordance with the performance design of the final lithographic printing plate precursor. The polymerizable compound is preferably used in the range of 5 to 75% by mass, more preferably 10 to 70% by mass, and particularly preferably 15 to 60% by mass with respect to the total solid content of the image recording layer.

<Other additives>
Moreover, the following compounds can also be included as another additive.

<Binder polymer>
As the binder polymer contained in the image recording layer of the present invention, those capable of supporting the image recording layer component on the support and being removable by a developer or on a printing machine are used. As the binder polymer, (meth) acrylic polymer, polyurethane resin, polyvinyl alcohol resin, polyvinyl butyral resin, polyvinyl formal resin, polyamide resin, polyester resin, epoxy resin and the like are used. In particular, (meth) acrylic polymers, polyurethane resins, and polyvinyl butyral resins are preferably used, and (meth) acrylic polymers, polyurethane resins, and polyvinyl butyral resins are more preferable.
In the present invention, “(meth) acrylic polymer” means (meth) acrylic acid, (meth) acrylic acid ester (alkyl ester, aryl ester, allyl ester, etc.), (meth) acrylamide and (meth) acrylamide derivatives. This refers to a copolymer having a (meth) acrylic acid derivative as a polymerization component. “Polyurethane resin” refers to a polymer produced by a condensation reaction of a compound having two or more isocyanate groups and a compound having two or more hydroxy groups. “Polyvinyl butyral resin” refers to a polymer synthesized by reacting polyvinyl alcohol and butyraldehyde obtained by saponifying part or all of polyvinyl acetate under an acidic condition (acetalization reaction). A polymer having an acid group or the like introduced by a method of reacting a compound having a remaining hydroxy group and an acid group or the like is also included.

A suitable example of the (meth) acrylic polymer used in the present invention includes a copolymer having a crosslinkable group. Here, the crosslinkable group is a group that crosslinks the binder polymer in the process of radical polymerization reaction that occurs in the image recording layer when the lithographic printing plate precursor is exposed. Although it will not specifically limit if it is a group of such a function, For example, an ethylenically unsaturated bond group, an amino group, an epoxy group etc. are mentioned as a functional group which can be addition-polymerized. Moreover, the functional group which can become a radical by light irradiation may be sufficient, and as such a crosslinkable group, a thiol group, a halogen group, etc. are mentioned, for example. Of these, an ethylenically unsaturated bond group is preferable. As the ethylenically unsaturated bond group, a styryl group, a (meth) acryloyl group, and an allyl group are preferable.
In the binder polymer, for example, free radicals (polymerization initiating radicals or growth radicals in the polymerization process of the polymerizable compound) are added to the crosslinkable functional group, and the addition polymerization is performed directly between the polymers or through the polymerization chain of the polymerizable compound. As a result, a cross-link is formed between the polymer molecules and cured. Alternatively, atoms in the polymer (eg, hydrogen atoms on carbon atoms adjacent to the functional bridging group) are abstracted by free radicals to form polymer radicals that are bonded together, thereby causing cross-linking between polymer molecules. Forms and cures.
The content of the crosslinkable group in the (meth) acrylic polymer (content of unsaturated double bond capable of radical polymerization by iodine titration) is preferably 0.01 to 10.0 mmol per 1 g of the binder polymer. Preferably it is 0.05-9.0 mmol, Most preferably, it is 0.1-8.0 mmol.

  The (meth) acrylic polymer in the present invention is preferably a copolymer having an acid group and / or a hydrophilic group. Examples of the acid group include a carboxylic acid group, a sulfonic acid group, a phosphonic acid group, a phosphoric acid group, and a sulfonamide group, and a carboxylic acid group is particularly preferable. As the repeating unit containing an acid group, a repeating unit derived from (meth) acrylic acid or one represented by the following general formula (I) is preferably used.

In general formula (I), R ¹ represents a hydrogen atom or a methyl group, and R ² represents a single bond or an n + 1 valent linking group. A represents an oxygen atom or —NR ³ —, and R ³ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. n represents an integer of 1 to 5.

The linking group represented by R ² in the general formula (I) is composed of an atomic group selected from a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom and a halogen atom, and the number of atoms is preferably Is 1-80. Specifically, an alkylene group, a substituted alkylene group, an arylene group, a substituted arylene group, and the like can be mentioned. These divalent groups are linked in multiples by any of an amide bond, an ether bond, a urethane bond, a urea bond, and an ester bond. You may have the structure made. R ² is a structure in which a single bond, an alkylene group, a substituted alkylene group, and an alkylene group and / or a substituted alkylene group are linked together by any one of an amide bond, an ether bond, a urethane bond, a urea bond, and an ester bond. Preferably, a single bond, an alkylene group having 1 to 5 carbon atoms, a substituted alkylene group having 1 to 5 carbon atoms, and an alkylene group having 1 to 5 carbon atoms and / or a substituted alkylene group having 1 to 5 carbon atoms is an amide bond. , An ether bond, a urethane bond, a urea bond, or an ester bond, and more preferably a structure in which a single bond, an alkylene group having 1 to 3 carbon atoms, a substituted alkylene group having 1 to 3 carbon atoms, And an alkylene group having 1 to 3 carbon atoms and / or a substituted alkylene group having 1 to 3 carbon atoms is an amide bond, ether bond, urethane bond, urea A structure in which a plurality of bonds and / or ester bonds are linked together is particularly preferable.

  Examples of the substituent include a monovalent nonmetallic atomic group excluding a hydrogen atom, a halogen atom (—F, —Br, —Cl, —I), a hydroxy group, a cyano group, an alkoxy group, an aryloxy group, Examples include a mercapto group, an alkylthio group, an arylthio group, an alkylcarbonyl group, an arylcarbonyl group, a carboxy group and its conjugated base group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an aryl group, an alkenyl group, and an alkynyl group.

R ³ is preferably a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, and particularly preferably a hydrogen atom or a methyl group. n is preferably 1 to 3, more preferably 1 or 2, and particularly preferably 1.

  The proportion (mol%) of the polymerization component having a carboxylic acid group in the total polymerization components of the (meth) acrylic polymer is preferably 1 to 70% from the viewpoint of developability. Considering compatibility between developability and printing durability, 1 to 50% is more preferable, and 1 to 30% is particularly preferable.

  Examples of the hydrophilic group include a hydroxy group, a carboxy group, an alkylene oxide structure, an amino group, an ammonium group, an amide group, a sulfo group, and a phosphoric acid group. Among them, an alkylene oxide unit having 2 or 3 carbon atoms An alkylene oxide structure having 1 to 9 is preferable. For imparting a hydrophilic group to the binder polymer, for example, copolymerization of a monomer having a hydrophilic group is performed.

  The (meth) acrylic polymer used in the present invention is a polymer of an alkyl (meth) acrylate or an aralkyl ester in addition to the above-described polymer unit having an acid group and / or hydrophilic group and a polymer unit having a crosslinkable group. It may have a unit, a polymer unit of (meth) acrylamide or a derivative thereof, a polymer unit of α-hydroxymethyl acrylate, or a polymer unit of a styrene derivative. The alkyl group of the (meth) acrylic acid alkyl ester is preferably an alkyl group having 1 to 5 carbon atoms and an alkyl group having the above-described substituent having 2 to 8 carbon atoms, and a methyl group is more preferable. Examples of (meth) acrylic acid aralkyl esters include benzyl (meth) acrylate. Examples of (meth) acrylamide derivatives include N-isopropylacrylamide, N-phenylmethacrylamide, N- (4-methoxycarbonylphenyl) methacrylamide, N, N-dimethylacrylamide, morpholinoacrylamide and the like. Examples of the α-hydroxymethyl acrylate include ethyl α-hydroxymethyl acrylate and cyclohexyl α-hydroxymethyl acrylate. Examples of styrene derivatives include styrene and 4-tertbutylstyrene.

As preferable examples of the polyurethane resin in the present invention, paragraph numbers [00099] to [0210] of JP-A No. 2007-187836, paragraph numbers [0019] to [0100] of JP-A No. 2008-276155, JP-A No. Examples include polyurethane resins described in paragraph numbers [0018] to [0107] of JP-A-2005-250438 and paragraph numbers [0021] to [0083] of JP-A-2005-250158.
As a suitable example of the polyvinyl butyral resin in this invention, the polyvinyl butyral resin as described in Paragraph Nos. [0006]-[0013] of Unexamined-Japanese-Patent No. 2001-75279 can be mentioned.

  A part of the acid groups in the binder polymer may be neutralized with a basic compound. Examples of basic compounds include basic nitrogen-containing compounds, alkali metal hydroxides, quaternary ammonium salts, and quaternary phosphonium salt hydroxides.

  The binder polymer used in the present invention varies depending on the use form of the lithographic printing plate precursor. In the case of a lithographic printing plate precursor using an alkaline developer having a pH of 8 or more, a binder having an acid group is preferred, and in the case of a lithographic printing plate precursor to be developed on a printing machine, a binder having a hydrophilic group is preferred.

The binder polymer has a mass average molar mass (Mw) of preferably 5000 or more, more preferably 10,000 to 300,000, and a number average molar mass (Mn) of preferably 1000 or more, and more preferably 2000 to 250,000. The polydispersity (Mw / Mn) is preferably 1.1-10.
A binder polymer may be used independently or may be used in mixture of 2 or more types.

The content of the binder polymer is preferably 5 to 75% by mass, more preferably 10 to 70% by mass with respect to the total solid content of the image recording layer, from the viewpoint of good image area strength and image formability. -60 mass% is still more preferable.
The total content of the polymerizable compound and the binder polymer is preferably 90% by mass or less with respect to the total solid content of the image recording layer. If it is 90 mass% or less, since a sensitivity and developability improve more, it may be preferable. More preferably, it is 35-80 mass%.

<Sensitizing dye>
The sensitizing dye used in the image recording layer is in an excited state by absorbing light at the time of image exposure, and imparts energy to the polymerization initiator by electron transfer, energy transfer or heat generation, and improves the polymerization initiation function. If there is no particular limitation, it can be used. In particular, a sensitizing dye having a maximum absorption in a wavelength range of 300 to 450 nm or 750 to 1400 nm is preferably used.

Examples of the sensitizing dye having the maximum absorption in the wavelength range of 350 to 450 nm include merocyanines, benzopyrans, coumarins, aromatic ketones, anthracenes, styryls, and oxazoles.
Of the sensitizing dyes having an absorption maximum in the wavelength range of 350 to 450 nm, a dye more preferable from the viewpoint of high sensitivity is a dye represented by the following general formula (IX).

In General Formula (IX), A represents an aryl group or a heteroaryl group which may have a substituent, and X represents an oxygen atom, a sulfur atom, or ═N (R ₃ ). R ₁ , R ₂ and R ₃ each independently represents a monovalent non-metallic atomic group, and A and R ₁ or R ₂ and R ₃ are bonded to each other to form an aliphatic or aromatic group. A ring may be formed.
General formula (IX) will be described in more detail. The monovalent nonmetallic atomic group represented by R ₁ , R ₂ or R ₃ is preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group. Represents a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, a hydroxy group, or a halogen atom.
The aryl group and heteroaryl group which may have a substituent represented by A are each a substituted or unsubstituted aryl group and a substituted or unsubstituted heteroaryl group represented by R ₁ , R ₂ and R ₃ , respectively. It is the same.

Specific examples of such a sensitizing dye include paragraph numbers [0047] to [0053] of JP-A No. 2007-58170, paragraph numbers [0036] to [0037] of JP-A No. 2007-93866, and JP-A No. 2007. The compounds described in paragraph Nos. [0042] to [0047] of JP-72816 are preferably used.
JP-A-2006-189604, JP-A-2007-171406, JP-A-2007-206216, JP-A-2007-206217, JP-A-2007-225701, JP-A-2007-225702, JP-A-2007-316582 The sensitizing dyes described in JP-A-2007-328243 are also preferably used.

Then, it describes about the sensitizing dye (henceforth an infrared absorber) which has maximum absorption in the wavelength range of 750-1400 nm. As the infrared absorber, a dye or a pigment is preferably used.
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 Is mentioned.
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 preferred, and particularly preferred examples include cyanine dyes represented by the following general formula (a).

In the general formula (a), X ¹ represents a hydrogen atom, a halogen atom, -X ² -L ¹ or a group shown below. Here, X ² represents an oxygen atom, —NL ² — or a sulfur atom, and L ¹ and L ² represent a hydrocarbon group, aryl group, hetero atom (N, S, O, halogen atom having 1 to 12 carbon atoms). , Se), an aryl group, and a hydrocarbon group having 1 to 12 carbon atoms including a hetero atom. Xa ^- is Za ^- described later is synonymous with. R ^a represents a hydrogen atom or a substituent selected from an alkyl group, an aryl group, a substituted or unsubstituted amino group, and a halogen atom.

R ¹ and R ² each independently represent a hydrocarbon group having 1 to 12 carbon atoms. In view of storage stability of the image recording layer coating solution, R ¹ and R ² are preferably hydrocarbon groups having 2 or more carbon atoms. R ¹ and R ² may be connected to each other to form a ring, and when a ring is formed, it is particularly preferable to form a 5-membered ring or a 6-membered ring.
Ar ¹ and Ar ² may be the same or different and each represents an aryl group which may have a substituent. Preferred aryl groups include a benzene ring group and a naphthalene ring group. Moreover, as a preferable substituent, a C12 or less hydrocarbon group, a halogen atom, and a C12 or less alkoxy group are mentioned. Y ¹ and Y ² may be the same or different and each represents a sulfur atom or a dialkylmethylene group having 12 or less carbon atoms. R ³ and R ⁴ 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 an alkoxy group having 12 or less carbon atoms, a carboxy group, and a sulfo group. R ⁵ , R ⁶ , R ⁷ and R ⁸ may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 12 or less carbon atoms. In view of easy availability of the raw material, 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 halide ion, a perchlorate ion, a tetrafluoroborate ion, a hexafluorophosphate ion and a sulfonate ion, particularly preferably a perchlorate ion, from the storage stability of the image recording layer coating solution. Hexafluorophosphate ion and aryl sulfonate ion.

Specific examples of the cyanine dye represented by the general formula (a) include compounds described in paragraph Nos. [0017] to [0019] of JP-A No. 2001-133969, paragraph Nos. [0016] of JP-A No. 2002-023360. ] To [0021], compounds described in paragraphs [0012] to [0037] of JP 2002-040638 A, preferably paragraphs [0034] to [0041] of JP 2002-278057 A, JP The compounds described in paragraphs [0080] to [0086] of 2008-195018, particularly preferably the compounds described in paragraphs [0035] to [0043] of JP-A-2007-90850 are exemplified.
In addition, compounds described in paragraph Nos. [0008] to [0009] of JP-A No. 5-5005 and paragraph numbers [0022] to [0025] of JP-A No. 2001-222101 can also be preferably used.

Only 1 type may be used for an infrared absorption dye, 2 or more types may be used together, and infrared absorbers other than infrared absorption dyes, such as a pigment, may be used together. As the pigment, the compounds described in JP-A-2008-195018, paragraphs [0072] to [0076] are preferable.
The content of the sensitizing dye is preferably 0.05 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, and particularly preferably 0.2 to 10 parts by mass with respect to 100 parts by mass of the total solid content of the image recording layer. Part by mass.

<Hydrophobic precursor>
The image recording layer may contain a hydrophobizing precursor in order to improve developability or on-press developability. The hydrophobized precursor means fine particles capable of converting the image recording layer to hydrophobic when heat and / or light is applied. The fine particles are at least one selected from hydrophobic thermoplastic polymer fine particles, heat-reactive polymer fine particles, polymer fine particles having a polymerizable group, microcapsules enclosing a hydrophobic compound, and microgel (crosslinked polymer fine particles). It is preferable. Among these, polymer fine particles and microgels having a polymerizable group are preferable.

Hydrophobic thermoplastic polymer fine particles include those disclosed in Research Disclosure, No. 1, January 1992. 333003, JP-A-9-123387, JP-A-9-131850, JP-A-9-171249, JP-A-9-171250, and European Patent No. 931647, etc. A fine particle can be mentioned as a suitable thing.
Specific examples of polymers constituting such polymer fine particles include ethylene, styrene, vinyl chloride, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, vinylidene chloride, acrylonitrile, vinyl carbazole, and polyalkylene structures. Mention may be made of homopolymers or copolymers of monomers such as acrylates or methacrylates or mixtures thereof. Among them, more preferable examples include a copolymer containing polystyrene, styrene and acrylonitrile, and polymethyl methacrylate.
The average particle diameter of the hydrophobic thermoplastic polymer fine particles used in the present invention is preferably 0.01 to 2.0 μm.

Examples of the heat-reactive polymer fine particles used in the present invention include polymer fine particles having a heat-reactive group, and these form a hydrophobized region by cross-linking by a heat reaction and a functional group change at that time.
The thermoreactive group in the polymer fine particles having a thermoreactive group used in the present invention may be any functional group that performs any reaction as long as a chemical bond is formed, but is preferably a polymerizable group, Examples include ethylenically unsaturated groups that undergo radical polymerization reactions (eg, acryloyl groups, methacryloyl groups, vinyl groups, allyl groups, etc.), cationic polymerizable groups (eg, vinyl groups, vinyloxy groups, epoxy groups, oxetanyl groups, etc.) ), An isocyanato group that performs an addition reaction or a block thereof, an epoxy group, a vinyloxy group, and a functional group having an active hydrogen atom that is a reaction partner thereof (for example, an amino group, a hydroxy group, a carboxy group, etc.), and a condensation reaction Carboxy group and reaction partner hydroxy group or amino group, acid anhydride and reaction phase for ring-opening addition reaction , And the like as a preferable amino group or a hydroxy group is.

As the microcapsules used in the present invention, for example, as described in JP-A Nos. 2001-277740 and 2001-277742, all or part of the constituent components of the image recording layer are encapsulated in the microcapsules. Is. The constituent components of the image recording layer can also be contained outside the microcapsules. Furthermore, it is preferable that the image recording layer containing the microcapsule includes a hydrophobic constituent component in the microcapsule and a hydrophilic constituent component outside the microcapsule.
The microgel used in the present invention can contain a part of the constituent components of the image recording layer in at least one of the inside and the surface thereof. In particular, an embodiment in which a reactive microgel is formed by having a radical polymerizable group on the surface thereof is particularly preferable from the viewpoint of image forming sensitivity and printing durability.

A known method can be applied to microencapsulate or microgel the constituent components of the image recording layer.
The average particle size of the microcapsule or microgel is preferably 0.01 to 3.0 μm, more preferably 0.05 to 2.0 μm, and particularly preferably 0.10 to 1.0 μm. Within this range, good resolution and stability over time can be obtained.
The content of the hydrophobizing precursor is preferably 5 to 90% by mass based on the total solid content of the image recording layer.

<Grease sensitizer>
The image recording layer of the present invention can contain a low molecular weight sensitizer such as a phosphonium compound and a nitrogen-containing low molecular weight compound in order to further improve the inking property.
Examples of the phosphonium compound include phosphonium compounds described in JP-A-2006-297907 and JP-A-2007-50660. Specific examples include tetrabutylphosphonium iodide, butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, 1,4-bis (triphenylphosphonio) butanedi (hexafluorophosphate), 1,7-bis (tri Phenylphosphonio) heptane sulfate, 1,9-bis (triphenylphosphonio) nonane = naphthalene-2,7-disulfonate, and the like.

  Examples of the nitrogen-containing low molecular weight compound include amine salts and quaternary ammonium salts. Also included are imidazolinium salts, benzoimidazolinium salts, pyridinium salts, and quinolinium salts. Of these, quaternary ammonium salts and pyridinium salts are preferred. Specific examples include tetramethylammonium = hexafluorophosphate, tetrabutylammonium = hexafluorophosphate, dodecyltrimethylammonium = p-toluenesulfonate, benzyltriethylammonium = hexafluorophosphate, benzyldimethyloctylammonium = hexafluorophosphate. Fert, benzyldimethyldodecyl ammonium = hexafluorophosphate, paragraph numbers [0021] to [0037] of JP 2008-284858 A, paragraph numbers [0030] to [0057] of JP 2009-90645 A Compound etc. are mentioned.

  The content of the sensitizing agent is preferably 0.01 to 30.0% by mass, more preferably 0.1 to 15.0% by mass, and more preferably 1 to 10.0% by mass with respect to the total solid content of the image recording layer. % Is more preferable.

<Low molecular hydrophilic compound>
The image recording layer in the invention may contain a low molecular weight hydrophilic compound in order to improve the on-press developability without reducing the printing durability.
As the low molecular weight hydrophilic compound, for example, as the water-soluble organic compound, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol and the like glycols and ether or ester derivatives thereof, glycerin, Polyols such as pentaerythritol and tris (2-hydroxyethyl) isocyanurate, organic amines such as triethanolamine, diethanolamine and monoethanolamine and salts thereof, organic sulfones such as alkylsulfonic acid, toluenesulfonic acid and benzenesulfonic acid Acids and salts thereof, organic sulfamic acids such as alkylsulfamic acid and salts thereof, organic sulfuric acids such as alkylsulfuric acid and alkylethersulfuric acid and salts thereof, phenylphosphonic acid Organic phosphonic acids and salts thereof, tartaric acid, oxalic acid, citric acid, malic acid, lactic acid, gluconic acid, organic carboxylic acids and salts thereof such as amino acids, betaines, and the like.
Among these, in the present invention, it is preferable to contain at least one selected from polyols, organic sulfates, organic sulfonates, and betaines.

  Specific examples of organic sulfonates include alkyl sulfonates such as sodium butyl sulfonate, sodium hexyl sulfonate, sodium 2-ethylhexyl sulfonate, sodium cyclohexyl sulfonate, and sodium octyl sulfonate; 5, 8, 11 -Sodium trioxapentadecane-1-sulfonate, sodium 5,8,11-trioxaheptadecane-1-sulfonate, sodium 13-ethyl-5,8,11-trioxaheptadecane-1-sulfonate, 5 , 8,11,14-tetraoxatetradecosane-1-alkyl sulfonate containing an ethylene oxide chain such as sodium sulfonate; sodium benzenesulfonate, sodium p-toluenesulfonate, sodium p-hydroxybenzenesulfonate , Sodium p-styrenesulfonate, dimethyl-5-sulfonate sodium isophthalate, sodium 1-naphthylsulfonate, sodium 4-hydroxynaphthylsulfonate, disodium 1,5-naphthalenedisulfonate, 1,3,6-naphthalene Aryl sulfonates such as trisodium trisulfonate, described in paragraph numbers [0026] to [0031] of JP 2007-276454 A, and paragraph numbers [0020] to [0047] of JP 2009-154525 A Compound etc. are mentioned. The salt may be a potassium salt or a lithium salt.

Organic sulfates include sulfates of alkyl, alkenyl, alkynyl, aryl or heterocyclic monoethers of polyethylene oxide. The number of ethylene oxide units is preferably 1 to 4, and the salt is preferably a sodium salt, potassium salt or lithium salt. Specific examples thereof include compounds described in paragraph numbers [0034] to [0038] of JP-A-2007-276454.
As the betaines, compounds having 1 to 5 carbon atoms of the hydrocarbon substituent on the nitrogen atom are preferable. Specific examples include trimethylammonium acetate, dimethylpropylammonium acetate, 3-hydroxy-4-trimethyl. Ammonioobylate, 4- (1-pyridinio) butyrate, 1-hydroxyethyl-1-imidazolioacetate, trimethylammonium methanesulfonate, dimethylpropylammonium methanesulfonate, 3-trimethylammonio-1-propanesulfonate, Examples include 3- (1-pyridinio) -1-propanesulfonate.

Since low molecular weight hydrophilic compounds have a small hydrophobic part structure and almost no surface activity, dampening water penetrates into the exposed part of the image recording layer (image part), reducing the hydrophobicity and film strength of the image part. The ink receptivity and printing durability of the image recording layer can be maintained well.
The content of the low molecular weight hydrophilic compound in the image recording layer is preferably 0.5 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 image recording layer. preferable. In this range, good on-press developability and printing durability can be obtained. A low molecular weight hydrophilic compound may be used independently and may be used in mixture of 2 or more types.

<Other ingredients>
The image recording layer preferably contains a chain transfer agent. The chain transfer agent is defined, for example, in Polymer Dictionary 3rd Edition (Edition of Polymer Society, 2005), pages 683-684. As the chain transfer agent, for example, a compound group having SH, PH, SiH, GeH in the molecule is used. These can donate hydrogen to low-activity radical species to generate radicals, or can be oxidized and then deprotonated to generate radicals. In the image recording layer of the present invention, in particular, thiol compounds (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzthiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles, etc.) Can be preferably used.
The content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 1 to 10 parts by mass, and particularly preferably 1 to 5 parts by mass with respect to 100 parts by mass of the total solid content of the image recording layer. is there.

  The image recording layer can further contain various additives as required. Additives include surfactants for promoting developability and improving the surface of the coating, hydrophilic polymers for improving developability and dispersion stability of microcapsules, and visual and non-image areas. Colorants and print-out agents, polymerization inhibitors for preventing unnecessary thermal polymerization of polymerizable compounds during production or storage of image recording layers, higher fat derivatives for preventing polymerization inhibition by oxygen, etc. Hydrophobic low molecular weight compounds, inorganic fine particles for improving the strength of the cured film in the image area, organic fine particles, co-sensitizers for improving sensitivity, plasticizers for improving plasticity, and the like. All of these compounds are known, for example, paragraph numbers [0161] to [0215] of JP-A-2007-206217, paragraph number [0067] of JP-T-2005-509192, and JP-A-2004-310000. The compounds described in paragraph numbers [0023] to [0026] and [0059] to [0066] of the gazette can be used. As for the surfactant, a surfactant which may be added to the developer described later can also be used.

<Formation of image recording layer>
The image recording layer of the present invention is formed by preparing and applying a coating solution by dispersing or dissolving each of the necessary image recording layer components in a solvent. Examples of the solvent used include 2-butanone, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-methoxyethyl acetate, 1-methoxy-2-propyl acetate, and γ-butyllactone. It is not limited to this. A solvent is used individually or in mixture. The solid content concentration of the coating solution is preferably 1 to 50% by mass.

The coating amount (solid content) of the image recording layer is preferably 0.3 to 3.0 g / m ² . Various methods can be used as a coating method. Examples thereof include bar coater coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating, and roll coating.

<Undercoat layer>
In the lithographic printing plate precursor according to the invention, an undercoat layer (sometimes referred to as an intermediate layer) is preferably provided between the image recording layer and the support. The undercoat layer enhances the adhesion between the support and the image recording layer in the exposed area, and easily peels off the image recording layer from the support in the unexposed area. Contributes to improvement. In the case of infrared laser exposure, the undercoat layer functions as a heat insulating layer, thereby preventing the heat generated by the exposure from diffusing to the support and reducing the sensitivity.

  As the compound used for the undercoat layer, those having an adsorptive group capable of being adsorbed on the surface of the support and a crosslinkable group for improving the adhesion to the image recording layer are preferable. Furthermore, compounds having a hydrophilicity-imparting group such as a sulfo group can also be mentioned as suitable compounds. These compounds may be low molecular weight or high molecular weight polymers. Moreover, you may use these compounds in mixture of 2 or more types as needed.

In the case of a high molecular polymer, a copolymer of a monomer having an adsorptive group, a monomer having a hydrophilic group, and a monomer having a crosslinkable group is preferable. The adsorbable adsorptive group to the surface of the support, a phenolic hydroxy group, a carboxy _{group, -PO 3 H 2, -OPO 3} H 2, -CONHSO 2 -, - SO 2 NHSO 2 -, - COCH 2 COCH 3 Is preferred. As the hydrophilic group, a sulfo group is preferable. The crosslinkable group is preferably a methacryl group or an allyl group.
This polymer may have a crosslinkable group introduced by salt formation between the polar substituent of the polymer, a substituent having a counter charge and a compound having an ethylenically unsaturated bond, Other monomers, preferably hydrophilic monomers, may be further copolymerized.

Specifically, a silane coupling agent having an addition-polymerizable ethylenic double bond reactive group described in JP-A-10-282679 and an ethylenic compound described in JP-A-2-304441. The phosphorus compound which has a heavy bond reactive group is mentioned suitably. Crosslinkable groups (preferably ethylenically unsaturated bond groups) described in JP-A-2005-238816, JP-A-2005-125649, JP-A-2006-239867, and JP-A-2006-215263 interact with the support surface. Those containing a low molecular or high molecular compound having a functional group and a hydrophilic group are also preferably used.
More preferable are polymer polymers having an adsorbable group, a hydrophilic group, and a crosslinkable group that can be adsorbed on the support surface described in JP-A Nos. 2005-125749 and 2006-188038.

The content of unsaturated double bonds in the polymer resin for the undercoat layer is preferably 0.1 to 10.0 mmol, and most preferably 0.2 to 5.5 mmol per 1 g of the polymer.
The polymer for the undercoat layer preferably has a mass average molar mass of 5000 or more, more preferably 10,000 to 1,000,000.

  The undercoat layer of the present invention comprises, in addition to the above undercoat compound, a chelating agent, a secondary or tertiary amine, a polymerization inhibitor, an amino group, or a functional group having a polymerization inhibiting ability, in order to prevent contamination over time. Compounds having a group that interacts with the surface of an aluminum support (for example, 1,4-diazabicyclo [2,2,2] octane (DABCO), 2,3,5,6-tetrahydroxy-p-quinone, chloranil , Sulfophthalic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylethylenediaminediacetic acid, hydroxyethyliminodiacetic acid, and the like.

The undercoat layer is applied by a known method. The coating amount (solid content) of the undercoat layer is preferably from 0.1-100 mg / m ^2, and more preferably 1 to 30 mg / m ^2.

<Support>
As the support used in the lithographic printing plate precursor according to the invention, a known support is used. Of these, an aluminum plate that has been roughened and anodized by a known method is preferred.
In addition, the above aluminum plate is optionally subjected to micropore enlargement treatment or sealing treatment of an anodized film described in JP-A Nos. 2001-253181 and 2001-322365, and US Pat. 714,066, 3,181,461, 3,280,734 and 3,902,734, or alkali metal silicates as described in U.S. Pat. Surface hydrophilization treatment with polyvinylphosphonic acid or the like as described in each specification of 3,276,868, 4,153,461 and 4,689,272 is appropriately performed and performed. be able to.

The support preferably has a center line average roughness of 0.10 to 1.2 μm.
The color density of the support is preferably from 0.15 to 0.65 in terms of the reflection density value. Within this range, good image formability by preventing halation during image exposure and good plate inspection after development can be obtained.

  The thickness of the support is preferably from 0.1 to 0.6 mm, more preferably from 0.15 to 0.4 mm, and even more preferably from 0.2 to 0.3 mm.

  If necessary, the support of the present invention includes an organic polymer compound described in JP-A-5-45885 and a silicon alkoxy compound described in JP-A-6-35174 on the back surface. A backcoat layer can be provided.

[Preparation method of lithographic printing plate]
A lithographic printing plate can be produced by subjecting the lithographic printing plate precursor according to the invention to image exposure and development or development on a printing machine.

<Image exposure>
The lithographic printing plate precursor is imagewise exposed by laser exposure through a transparent original image having a line image, a halftone dot image or the like, or by laser beam scanning by digital data.
The wavelength of the light source is preferably 300 to 450 nm or 750 to 1400 nm. In the case of a light source of 300 to 450 nm, a lithographic printing plate precursor having a sensitizing dye having an absorption maximum in this wavelength region in the image recording layer is preferably used, and in the case of a light source of 750 to 1400 nm, absorption is performed in this wavelength region. A lithographic printing plate precursor containing an infrared absorbing agent, which is a sensitizing dye, in the image recording layer is preferably used. As the light source of 300 to 450 nm, a semiconductor laser is suitable. As a light source of 750 to 1400 nm, a solid laser and a semiconductor laser emitting infrared rays are suitable. Regarding the infrared laser, the output is preferably 100 mW or more, the exposure time per pixel is preferably within 20 microseconds, and the irradiation energy amount is preferably 10 to 300 mJ / cm ² . In order to shorten the exposure time, it is preferable to use a multi-beam laser device. The exposure mechanism may be any of an internal drum system, an external drum system, a flat bed system, and the like.
Image exposure can be performed by a conventional method using a plate setter or the like. In the case of on-press development, the lithographic printing plate precursor may be mounted on a printing press and then image exposure may be performed on the printing press.

<Development processing>
The development processing is (1) a method of developing with a developer having a pH of 2 to 14 (developer processing method), or (2) a method of developing on a printing press while adding dampening water and / or ink ( (On-press development system).

<Developer processing method>
In the developer processing method, the lithographic printing plate precursor subjected to image exposure is processed with a developer having a pH of 2 to 14, and the image recording layer in the non-exposed portion is removed to prepare a lithographic printing plate.
In development processing using a highly alkaline developer (pH 14 or higher), the protective layer is usually removed by a pre-water washing step, then alkali development is performed, the alkali is washed and removed by a post-water washing step, gum treatment is performed, and drying is performed. A lithographic printing plate is produced by drying in the process.
According to a preferred embodiment of the present invention, a developer having a pH of 8 to 12 is used. In this embodiment, it is preferable that a surfactant or a water-soluble polymer compound is contained in the developer, whereby the development and the gum solution treatment can be performed simultaneously. Therefore, the post-water washing step is not particularly required, and the development-gum solution treatment can be performed with one solution. Further, no pre-water washing step is required, and the protective layer can be removed simultaneously with the development-gum solution treatment. After the development-gum treatment, for example, it is preferable to perform drying after removing excess developer using a squeeze roller.

  The anionic surfactant used in the developer of the present invention is not particularly limited, but fatty acid salts, abietic acid salts, hydroxyalkanesulfonic acid salts, alkanesulfonic acid salts, dialkylsulfosuccinic acid salts, linear alkylbenzenesulfonic acid salts. Branched alkylbenzene sulfonates, alkyl naphthalene sulfonates, alkyl diphenyl ether (di) sulfonates, alkylphenoxy polyoxyethylene alkyl sulfonates, polyoxyethylene alkyl sulfophenyl ether salts, N-alkyl-N-oleyl taurine Sodium, N-alkylsulfosuccinic acid monoamide disodium salt, petroleum sulfonate, sulfated castor oil, sulfated beef tallow oil, fatty acid alkyl ester sulfate ester salt, alkyl Acid ester salts, polyoxyethylene alkyl ether sulfates, fatty acid monoglyceride sulfates, polyoxyethylene alkylphenyl ether sulfates, polyoxyethylene styryl phenyl ether sulfates, alkyl phosphate esters, polyoxyethylene alkyl ether phosphates Ester salts, polyoxyethylene alkylphenyl ether phosphate ester salts, saponified saponified styrene-maleic anhydride copolymers, partially saponified olefin-maleic anhydride copolymers, naphthalene sulfonate formalin condensates, etc. Is mentioned. Of these, alkylbenzene sulfonates, alkylnaphthalene sulfonates, and alkyl diphenyl ether (di) sulfonates are particularly preferably used.

  Although it does not specifically limit as a cationic surfactant used for the developing solution of this invention, A conventionally well-known thing can be used. Examples thereof include alkylamine salts, quaternary ammonium salts, alkyl imidazolinium salts, polyoxyethylene alkylamine salts, and polyethylene polyamine derivatives.

  The nonionic surfactant used in the developer of the present invention is not particularly limited, but is a polyethylene glycol type higher alcohol ethylene oxide adduct, alkylphenol ethylene oxide adduct, alkyl naphthol ethylene oxide adduct, phenol ethylene oxide adduct. , Naphthol ethylene oxide adduct, fatty acid ethylene oxide adduct, polyhydric alcohol fatty acid ester ethylene oxide adduct, higher alkylamine ethylene oxide adduct, fatty acid amide ethylene oxide adduct, fat and oil ethylene oxide adduct, polypropylene glycol ethylene oxide addition Dimethylsiloxane-ethylene oxide block copolymer, dimethylsiloxane- (propylene oxide-ethylene oxide) Id) block copolymer, fatty acid ester of polyhydric alcohol type glycerol, fatty acid ester of pentaerythritol, fatty acid ester of sorbitol and sorbitan, fatty acid ester of sucrose, alkyl ether of polyhydric alcohol, fatty acid amide of alkanolamines, etc. It is done. Among these, those having an aromatic ring and an ethylene oxide chain are preferable, and an alkyl-substituted or unsubstituted phenol ethylene oxide adduct or an alkyl-substituted or unsubstituted naphthol ethylene oxide adduct is more preferable.

  The zwitterionic surfactant used in the developer of the present invention is not particularly limited, and examples thereof include amine oxides such as alkyldimethylamine oxide, betaines such as alkylbetaine, and amino acids such as sodium alkylamino fatty acid. . In particular, alkyldimethylamine oxide which may have a substituent, alkylcarboxybetaine which may have a substituent, and alkylsulfobetaine which may have a substituent are preferably used. Specifically, the compound represented by the formula (2) in paragraph [0256] of JP-A-2008-203359, the formula (I) and the formula (II) in paragraph [0028] of JP-A-2008-276166 are disclosed. ), A compound represented by the formula (VI), and compounds represented by paragraph numbers [0022] to [0029] of JP-A-2009-47927 can be used.

  Two or more surfactants may be used in the developer. 0.01-20 mass% is preferable and, as for the quantity of surfactant contained in a developing solution, 0.1-10 mass% is more preferable.

Examples of the water-soluble polymer compound used in the developer of the present invention include soybean polysaccharide, modified starch, gum arabic, dextrin, fiber derivatives (eg, carboxymethyl cellulose, carboxyethyl cellulose, methyl cellulose, etc.) and modified products thereof, pullulan, polyvinyl Alcohol and derivatives thereof, polyvinylpyrrolidone, polyacrylamide and acrylamide copolymer, vinyl methyl ether / maleic anhydride copolymer, vinyl acetate / maleic anhydride copolymer, styrene / maleic anhydride copolymer, polyvinyl sulfonic acid and The salt, polystyrene sulfonic acid, its salt, etc. are mentioned.
A well-known thing can be used for the said soybean polysaccharide, for example, there exists a brand name Soya Five (made by Fuji Oil Co., Ltd.) as a commercial item, and the thing of various grades can be used. What can be preferably used is one in which the viscosity of a 10% by mass aqueous solution is in the range of 10 to 100 mPa / sec.
As the modified starch, known ones can be used. For example, starch such as corn, potato, tapioca, rice, wheat etc. is decomposed with acid or enzyme in the range of 5-30 glucose residues per molecule, and further alkali It can be made by a method of adding oxypropylene in the inside.

  Two or more water-soluble polymer compounds may be used in combination in the developer. The content of the water-soluble polymer compound in the developer is preferably from 0.1 to 20% by mass, and more preferably from 0.5 to 10% by mass.

The developer used in the present invention may contain a pH buffer. The developer of the present invention can be used without particular limitation as long as it is a buffering agent that exhibits a buffering action at a pH of 2 to 14. In the present invention, weakly alkaline buffering agents are preferably used. For example, (a) carbonate ions and hydrogen carbonate ions, (b) borate ions, (c) water-soluble amine compounds and ions of the amine compounds, and their Combination use etc. are mentioned. That is, for example, a combination of (a) carbonate ion-bicarbonate ion, (b) borate ion, or (c) water-soluble amine compound-amine compound ion exhibits pH buffering action in the developer. Even when the developer is used for a long period of time, fluctuations in pH can be suppressed, and therefore, development loss due to fluctuations in pH, development debris generation, and the like can be suppressed. Particularly preferred is a combination of carbonate ions and bicarbonate ions.
In order for carbonate ions and bicarbonate ions to be present in the developer, carbonate and bicarbonate may be added to the developer, or by adjusting the pH after adding carbonate or bicarbonate, Ions and bicarbonate ions may be generated. The carbonate and bicarbonate are not particularly limited, but are preferably alkali metal salts. Examples of the alkali metal include lithium, sodium, and potassium, and sodium is particularly preferable. Alkali metals may be used alone or in combination of two or more.
The total amount of carbonate ions and bicarbonate ions is preferably 0.05 to 5 mol / L, more preferably 0.07 to 2 mol / L, and particularly preferably 0.1 to 1 mol / L with respect to the developer.

  The developer of the present invention may contain an organic solvent. Examples of the organic solvent that can be contained include aliphatic hydrocarbons (hexane, heptane, Isopar E, H, G (manufactured by Esso Chemical Co., Ltd.)), aromatic hydrocarbons (toluene, xylene, etc.), halogens, and the like. Hydrocarbons (methylene dichloride, ethylene dichloride, trichlene, monochlorobenzene, etc.) and polar solvents. Examples of polar solvents include alcohols (methanol, ethanol, propanol, isopropanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, 1 -Nonanol, 1-decanol, benzyl alcohol, ethylene glycol monomethyl ether, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl Ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether Ter, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, methylphenyl carbinol, amyl alcohol, methyl amyl alcohol, etc.), ketones (acetone, 2-butanone, ethyl butyl ketone, methyl isobutyl ketone) , Cyclohexanone, etc.), esters (ethyl acetate, propyl acetate, butyl acetate, amyl acetate, benzyl acetate, methyl lactate, butyl lactate, ethylene glycol monobutyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol acetate, diethyl phthalate, butyl levulinate Etc.), other (triethyl phosphate, tricresyl phosphate, N-phenylethanolamine, N-phenyl) Alkenyl diethanolamine, N- methyldiethanolamine, N- ethyldiethanolamine, 4- (2-hydroxyethyl) morpholine, N, N- dimethylacetamide, N- methylpyrrolidone and the like) and the like.

  Two or more organic solvents can be used in combination in the developer. When the organic solvent is insoluble in water, it can be used after being solubilized in water using a surfactant or the like. When the developer contains an organic solvent, the concentration of the organic solvent is preferably less than 40% by mass from the viewpoint of safety and flammability.

  In addition to the above components, the developer of the present invention may contain preservatives, chelate compounds, antifoaming agents, organic acids, inorganic acids, inorganic salts, and the like. Specifically, compounds described in paragraph numbers [0266] to [0270] of JP-A-2007-206217 can be preferably used.

  The developer treatment of the lithographic printing plate precursor according to the invention is carried out in accordance with a conventional method at a temperature of 0 to 60 ° C., preferably about 15 to 40 ° C., for example, by immersing the exposed lithographic printing plate precursor in a developer and brushing It can be carried out by a method of rubbing with a brush, a method of spraying a developer by spraying and rubbing with a brush.

  In the present invention, the development treatment with a developer having a pH of 2 to 14 can be preferably carried out by an automatic development processor equipped with a developer supply means and a rubbing member. An automatic developing processor using a rotating brush roll as the rubbing member is particularly preferable. Further, the automatic processor preferably includes a means for removing excess developer such as a squeeze roller and a drying means such as a warm air device after the development processing means. Further, the automatic development processor may be provided with a preheating means for heat-treating the lithographic printing plate precursor after image exposure before the development processing means.

  The developer of the present invention can be used as a developer and a development replenisher for an exposed lithographic printing plate precursor. Further, the present invention can be preferably applied to the automatic developing processor as described above. When developing using an automatic developing processor, the developing solution becomes fatigued according to the amount of processing, so that the processing capability may be restored by using a replenishing solution or a fresh developing solution.

<On-press development method>
In the on-press development system, an image-exposed lithographic printing plate precursor is supplied with oil-based ink and an aqueous component on a printing machine, and the image recording layer in the non-image area is removed to produce a lithographic printing plate.
In other words, after image exposure of the lithographic printing plate precursor, it is mounted on the printing machine without any development processing, or after the lithographic printing plate precursor is mounted on the printing machine, image exposure is performed on the printing machine. When printing is performed by supplying the oil-based ink and the aqueous component, the uncured image recording layer is dissolved or dispersed in the non-image area by the supplied oil-based ink and / or the aqueous component in the initial stage of printing. And a hydrophilic surface is exposed at the portion. On the other hand, in the exposed portion, the image recording layer cured by exposure forms an oil-based ink receiving portion having a lipophilic surface. Oil-based ink or water-based component may be first supplied to the plate surface, but oil-based ink is supplied first in order to prevent the water-based component from being contaminated by the removed image recording layer component. Is preferred. In this way, the lithographic printing plate precursor is subjected to on-press development on a printing machine and used as it is for printing a large number of sheets. As the oil-based ink and the aqueous component, ordinary lithographic printing ink and fountain solution are preferably used.

  In the method of preparing a lithographic printing plate from the lithographic printing plate precursor according to the present invention, the entire lithographic printing plate precursor is exposed before exposure, during exposure, and from exposure to development, regardless of the development method. You may heat. By such heating, an image forming reaction in the image recording layer is promoted, and advantages such as improvement in sensitivity and printing durability and stabilization of sensitivity may occur. In the case of the developer processing method, it is also effective to perform whole surface post-heating or whole surface exposure on the image after the development processing for the purpose of improving the image strength and printing durability. Usually, heating before development is preferably performed under a mild condition of 150 ° C. or less. If the temperature is too high, problems such as curing of the non-image area may occur. Very strong conditions are used for heating after development. Usually, it is the range of 100-500 degreeC. If the temperature is low, sufficient image reinforcing action cannot be obtained. If the temperature is too high, problems such as deterioration of the support and thermal decomposition of the image area may occur.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these. In the polymer compound, the molecular weight is a mass average molar mass (Mw), and the ratio of repeating units is a mole percentage, except for those specifically defined.

[Synthesis examples of specific compounds]

Synthesis of Specific Compound (P-1) A In a 300 mL three-necked flask, 71.1 g of a methanol / water (80/20 mass ratio) mixed solution was weighed and heated to 50 ° C. Nitrogen was allowed to flow through the reaction vessel (flow rate: 100 mL / min), and stirring was continued for 30 minutes. In this reaction vessel, acrylamide: 35.54 g dissolved in methanol / water (80/20 mass ratio): 35.55 g solution A and VA-046B (manufactured by Wako Pure Chemical Industries, Ltd., water-soluble azo polymerization) Initiator): Solution B prepared by dissolving 1.93 g and 2-dimethylaminoethanethiol hydrochloride: 4.25 g in a methanol / water (80/20 mass ratio) mixed solution: 35.55 g was added dropwise at the same time. The dropping speed was set so that the total amount of each of the solution A and the solution B was dropped in 2.5 hours. After completion of dropping, the mixture was stirred for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and the reaction solution was added dropwise to 1 L of well-stirred ethyl acetate. After completion of the dropwise addition, the mixture was stirred for 30 minutes, and then allowed to stand to precipitate the precipitated solid. The supernatant was discarded, and 500 mL of ethyl acetate was added to the residue and stirred for 30 minutes. The solid deposited upon standing was precipitated, and the supernatant was discarded. The resulting solid was dried at room temperature under reduced pressure.
The solid thus obtained: 30 g was weighed into a 200 mL three-necked flask and dissolved in methanol: 60 g. To this solution, 4.36 g of a 28 mass% methanol solution of sodium methoxide was added and stirring was continued for 10 minutes. Furthermore, 5.48 g of methyl p-toluenesulfonate was added, and stirring was continued under methanol reflux until no amine in the reaction solution was detected by hydrochloric acid titration. When the reaction was stopped, methyl p-toluenesulfonate was added to continue the reaction. After completion of the reaction, the reaction solution was cooled to room temperature, and the reaction solution was added dropwise to 1 L of well-stirred ethyl acetate. After completion of the dropwise addition, the mixture was stirred for 30 minutes, and then allowed to stand to precipitate the precipitated solid. The supernatant was discarded, and 500 mL of ethyl acetate was added to the residue and stirred for 30 minutes. The solid deposited upon standing was precipitated, and the supernatant was discarded. The obtained solid was dried at room temperature under reduced pressure to obtain the specific compound (P-1) A.
The specific compound (P-1) A thus obtained was Mw: 1200.
(* VA-046B: 2,2′-azobis [2- (2-imidazolin-2-yl) propane] disulfate dihydrate)

Synthesis of Specific Compound (P-1) B to H By appropriately changing the amount of 2-dimethylaminoethanethiol hydrochloride, the amount of VA-046B, the amount of methanol / water mixture during polymerization and the polymerization temperature, Similarly, specific compounds (P-1) B to H were synthesized. Mw of the obtained specific compounds (P-1) B to H is shown in Table 1 below.

Synthesis of Specific Compound (P-2) A specific compound (P-2) (Mw: 1200) was obtained in the same manner as the specific compound (P-1) A except that acrylamide was changed to dimethylacrylamide.

Synthesis of Specific Compound (P-3) In a 300 mL three-necked flask, 79.22 g of a methanol / water (80/20 mass ratio) mixed solution was weighed and heated to 50 ° C. Nitrogen was allowed to flow through the reaction vessel (flow rate: 100 mL / min), and stirring was continued for 30 minutes. In this reaction vessel, A and VA-046B (Wako Pure) were prepared by dissolving 33.41 g of acrylamide and 6.20 g of acrylaminopropyltrimethylammonium chloride in 39.61 g of a methanol / water (80/20 mass ratio) mixed solution. (Manufactured by Yakuhin) Solution B prepared by dissolving 1.93 g and isobutyl mercaptan: 2.71 g in a methanol / water (80/20 mass ratio) mixed solution: 39.61 g was added dropwise at the same time. The dropping speed was set so that the total amount of each of the solution A and the solution B was dropped in 2.5 hours. After completion of dropping, the mixture was stirred for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and the reaction solution was added dropwise to 1 L of well-stirred ethyl acetate. After completion of the dropwise addition, the mixture was stirred for 30 minutes, and then allowed to stand to precipitate the precipitated solid. The supernatant was discarded, and 500 mL of ethyl acetate was added to the residue and stirred for 30 minutes. The solid deposited upon standing was precipitated, and the supernatant was discarded. The obtained solid was dried at room temperature under reduced pressure to obtain the specific compound (P-3).
The specific compound (P-3) thus obtained was Mw: 1300.

Synthesis of specific compound (P-4) The specific compound (P-4) (Mw: 1300) is the same as the specific compound (P-3) except that acrylamide is changed to dimethylacrylamide and the amount of isobutyl mercaptan is changed. Got.

Synthesis of Specific Compound (P-5) The specific compound (P-1) A was prepared in the same manner as the specific compound (P-1) A except that acrylamide was changed to N-isopropylacrylamide and the amount of 2-dimethylaminoethanethiol hydrochloride was changed. P-5) (Mw: 1300) was obtained.

Synthesis of Specific Compound (P-6) The specific compound (P-1) A was prepared in the same manner as the specific compound (P-1) A except that acrylamide was changed to N-acryloylmorpholine and the amount of 2-dimethylaminoethanethiol hydrochloride was changed. P-6) (Mw: 1300) was obtained.

Synthesis of Specific Compound (P-7) Specific Compound (P-7) (Mw: Mw :) except that acrylamide was changed to N-isopropylacrylamide and the amount of isobutyl mercaptan was changed. 1200).

Synthesis of Specific Compound (P-8) Specific Compound (P-8) (Mw: Mw :) except that acrylamide was changed to N-acryloylmorpholine and the amount of isobutyl mercaptan was changed. 1200).

Synthesis of specific compound (P-9) The specific compound (P-9) is the same as the specific compound (P-2) except that 2-dimethylaminoethanethiol hydrochloride is changed to 3-dimethylaminopropanethiol hydrochloride. (Mw: 1200) was obtained.

Synthesis of specific compound (P-10) The specific compound (P-10) (Mw: 1200) was the same as the specific compound (P-2) except that methyl p-toluenesulfonate was changed to propyl p-toluenesulfonate. )

Synthesis of specific compound (P-11) The specific compound (P-1211) (Mw: 1300) was the same as the specific compound (P-2) except that methyl p-toluenesulfonate was changed to pentyl p-toluenesulfonate. )

Synthesis of specific compound (P-12) A specific compound (P-12) (Mw: 1300) was obtained in the same manner as the specific compound (P-2) except that methyl p-toluenesulfonate was changed to benzyl bromide. .

Synthesis of specific compound (P-13) The specific compound (P-1) except that acrylamide was changed to 17.77 g and methyl acrylate: 21.52 g, and the amount of 2-dimethylaminoethanethiol hydrochloride was changed. ) A specific compound (P-13) (Mw: 1100) was obtained in the same manner as A.

Synthesis of specific compound (P-14) The specific compound (P-14) except that acrylamide was changed to 28.43 g and t-butyl acrylate: 12.82 g, and the amount of 2-dimethylaminoethanethiol hydrochloride was changed. -1) In the same manner as A, the specific compound (P-14) (Mw: 1200) was obtained.

Synthesis of specific compound (P-15) The specific compound (P-15) except that acrylamide was changed to 33.76 g of acrylamide and 4.61 g of 2-ethylhexyl acrylate, and the amount of 2-dimethylaminoethanethiol hydrochloride was changed. -1) The specific compound (P-15) (Mw: 1200) was obtained in the same manner as A.

Synthesis of specific compound (P-16) Acrylamide was changed to 44.61 g and methyl acrylate: 4.30 g, and the amount of 2-dimethylaminoethanethiol hydrochloride was changed. 1) In the same manner as A, the specific compound (P-16) (Mw: 1200) was obtained.

Synthesis of Specific Compound (P-17) The specific compound (P) except that acrylamide was changed to N-acryloylmorpholine: 56.47 g and methyl acrylate: 8.61 g, and the amount of 2-dimethylaminoethanethiol hydrochloride was changed. P-1) In the same manner as A, the specific compound (P-17) (Mw: 1100) was obtained.

[Synthesis example of organoclay complex]

Synthesis of organoclay complex (1) A Somasif ME-100 (manufactured by Coop Chemical): 1 g was added to 20 g of ion-exchanged water and heated to 50 ° C. A solution prepared by dissolving 1.79 g of the specific compound (P-1) A in 20 g of ion-exchanged water was added to this solution. The reaction solution was centrifuged to precipitate the solid, the supernatant was removed, and the residue was thoroughly washed with 20 g of ion exchange water. The residue was dried under reduced pressure to obtain an organoclay complex (1) A. As a result of analyzing the obtained organoclay composite (1) A by thermogravimetric analysis (TGA), the specific compound (P-1) A content in the organoclay composite (1) A is 62.0% by mass. there were.

Synthesis of organoclay complex (1) B to H Organics similar to organoclay complex (1) A except that specific compound (P-1) A was changed to specific compounds (P-1) B to H Clay composites (1) B to H were synthesized. The specific compound (P-1) B to H content of the obtained organoclay composite (1) B to H was as shown in Table 2 below.

Synthesis of organoclay complex (2) to (17) Same as organoclay complex (1) except that specific compound (P-1) A was changed to specific compounds (P-2) to (P-17) Thus, organoclay composites (2) to (17) were synthesized. As a result of analyzing the obtained organoclay complex by TGA, the specific compound contents of the organoclay complexes (2) to (17) were as shown in Table 3 below.

Synthesis of organoclay complex (18) An organoclay complex (18) was synthesized in the same manner as the organoclay complex (2) except that Somasif ME-100 was changed to Lucentite SWN (Coop Chemical). As a result of analyzing the obtained organoclay composite (18) by TGA, the specific compound (P-2) content of the organoclay composite (18) was 57.4% by mass.

Synthesis of organoclay complex (19) An organoclay complex (19) was synthesized in the same manner as the organoclay complex (2) except that Somasif ME-100 was changed to Kunipia F (Kunimine Industries). As a result of analyzing the obtained organoclay complex (19) by TGA, the specific compound (P-2) content of the organoclay complex (19) was 59.5% by mass.

Synthesis of organoclay complex (20) An organoclay complex (20) was synthesized in the same manner as the organoclay complex (2) except that Somasif ME-100 was changed to Kunipia W (Kunimine Industries). As a result of analyzing the obtained organoclay composite (20) by TGA, the specific compound (P-2) content of the organoclay composite (20) was 55.1% by mass.

Synthesis of organoclay complex (21) An organoclay complex (21) was synthesized in the same manner as the organoclay complex (2) except that Somasif ME-100 was changed to Smecton SA (manufactured by Kunimine Industries). As a result of analyzing the obtained organoclay composite (21) by TGA, the specific compound (P-2) content of the organoclay composite (21) was 49.0% by mass.

Synthesis of organoclay complex (22) An organoclay complex (22) was synthesized in the same manner as the organoclay complex (2) except that Somasif ME-100 was changed to NTS-10 (manufactured by Topy Industries). As a result of analyzing the obtained organoclay complex (22) by TGA, the specific compound (P-2) content of the organoclay complex (22) was 61.9% by mass.

Synthesis of the organoclay complex (23) The organoclay complex (23) was synthesized in the same manner as the organoclay complex (2) except that Somasif ME-100 was changed to NHT-sol B2 (Topy Industries). . As a result of analyzing the obtained organoclay composite (23) by TGA, the specific compound (P-2) content of the organoclay composite (23) was 57.5% by mass.

Synthesis of organoclay complex (24) 15 g of synthetic swellable mica synthesized by the following method was dispersed in 500 ml of ion-exchanged water to prepare a suspension. 300 ml of an aqueous solution in which 16 g of the specific compound (P-2) was dissolved was added to the swellable mica suspension and reacted at room temperature for 2 hours with stirring. The product was subjected to solid-liquid separation and washing to remove by-product salts, and then dried to obtain an organoclay complex (24). The specific organic compound (P-2) content of the obtained organoclay composite was 48.6% by mass.

Synthesis of swellable mica According to the method described in JP-A-2-149415, pulverized product of 13.5 g of talc and 2.5 g of sodium silicofluoride is mixed and heat-treated at 800 ° C. to swell the compound. 15.0 g of mica was obtained. The synthetic swellable mica had a cation exchange capacity of 70 meq / 100 g.

Organic clay complex (25)
An organic clay complex (25) was synthesized in the same manner as the organic clay complex (24) except that the specific compound (P-2) was changed to the following compound (C) [compound described in Patent Document 8]. As a result of analyzing the obtained organoclay composite (25) by TGA, the content of the compound (C) in the organoclay composite (25) was 52.1% by mass.

Organic clay complex (26)
An organoclay complex (26) was synthesized in the same manner as the organoclay complex (24) except that the specific compound (P-2) was changed to the following compound (D) [compound described in Patent Document 8]. As a result of analyzing the obtained organoclay composite (26) by TGA, the content of the compound (C) in the organoclay composite (26) was 31.1% by mass.

[Preparation and evaluation of lithographic printing plate precursor]

[Examples 1-8 and Comparative Examples 1-2]

(Production of support)
In order to remove rolling oil on the surface of an aluminum plate (material 1050) having a thickness of 0.3 mm, a degreasing treatment was performed at 50 ° C. for 30 seconds using a 10 mass% sodium aluminate aqueous solution, and then the hair diameter was 0.3 mm. The surface of the aluminum plate was grained using three bundle-planted nylon brushes and a pumice-water suspension (specific gravity 1.1 g / cm ³ ) having a median diameter of 25 μm and washed well with water. This plate was etched by being immersed in a 25 mass% aqueous sodium hydroxide solution at 45 ° C for 9 seconds, washed with water, further immersed in a 20 mass% nitric acid aqueous solution at 60 ° C for 20 seconds, and washed with water. The etching amount of the grained surface at this time was about 3 g / m ² .
Next, an electrochemical roughening treatment was performed continuously using an alternating voltage of 60 Hz. The electrolytic solution at this time was a 1% by mass nitric acid aqueous solution (containing 0.5% by mass of aluminum ions) and a liquid temperature of 50 ° C. The AC power source waveform is electrochemical roughening treatment using a trapezoidal rectangular wave alternating current with a time ratio TP of 0.8 msec until the current value reaches a peak from zero, a duty ratio of 1: 1, and a trapezoidal rectangular wave alternating current. Went. Ferrite was used for the auxiliary anode. The current density was 30 A / dm ² at the peak current value, and 5% of the current flowing from the power source was shunted to the auxiliary anode. The amount of electricity in nitric acid electrolysis was 175 C / dm ² when the aluminum plate was the anode. Then, water washing by spraying was performed.
Next, a 0.5% by mass hydrochloric acid aqueous solution (containing 0.5% by mass of aluminum ions) and an electrolytic solution having a liquid temperature of 50 ° C. and nitric acid electrolysis under the condition of an electric quantity of 50 C / dm ² when the aluminum plate is an anode. In the same manner as above, an electrochemical surface roughening treatment was performed, followed by washing with water by spraying. The plate was provided with a DC anodized film of 2.5 g / m ² at a current density of 15 A / dm ² using a 15% by mass sulfuric acid aqueous solution (containing 0.5% by mass of aluminum ions) as an electrolyte, then washed with water and dried. A support was used. The centerline average roughness (Ra) of this substrate was measured using a needle having a diameter of 2 μm and found to be 0.51 μm.

(Preparation of lithographic printing plate precursor 1)
The following undercoat layer coating solution (1) was applied to the above support so that the dry coating amount was 10 mg / m ² to prepare a support having an undercoat layer.

Undercoat layer coating solution (1)
・ Undercoat layer compound (1) (Mw: 60,000) 0.017 g
・ Methanol 9.00 g
・ Water 1.00g

On the undercoat layer, an image recording layer coating solution (1) having the following composition was bar-coated, followed by oven drying at 100 ° C. for 60 seconds to form an image recording layer having a dry coating amount of 1.0 g / m ² . Subsequently, a protective layer coating solution (1) having the following composition is bar-coated on the image recording layer and oven-dried at 120 ° C. for 60 seconds to form a protective layer having a dry coating amount of 0.15 g / m ^2. Thus, a lithographic printing plate precursor 1 (for Comparative Example 1) was obtained.

Image recording layer coating solution (1)
-Binder polymer (1) The following structure (Mw 90,000) 0.162g
-Polymerization initiator I-13 The following structure 0.100g
・ Infrared absorber (1) 0.020 g of the following structure
Polymerizable compound, Aronix M-215
(Toa Gosei Co., Ltd., isocyanuric acid EO-modified diacrylate) 0.385 g
Fluorosurfactant (1) The following structure (Mw: 10,000) 0.044 g
・ 2-butanone 1.091g
・ 1-methoxy-2-propanol 8.609g
・ Water 2.425g
-Microgel aqueous dispersion (1) synthesized as follows: 2.640 g

Synthesis of Microgel Water Dispersion (1) As an oil phase component, 10 g of trimethylolpropane and xylene diisocyanate adduct (Mitsui Chemicals, Takenate D-110N, 75 mass% ethyl acetate solution), Aronix M-215 6.00 g (manufactured by Toagosei Co., Ltd.) and 0.12 g of Pionein A-41C (manufactured by Takemoto Yushi Co., Ltd.) were dissolved in 16.67 g of ethyl acetate. As an aqueous phase component, 37.5 g of a 4 mass% aqueous solution of polyvinyl alcohol (PVA-205 manufactured by Kuraray Co., Ltd.) was prepared. The oil phase component and the aqueous phase component were mixed and emulsified for 10 minutes at 12000 rpm using a homogenizer. The obtained emulsion was added to 25 g of distilled water, stirred at room temperature for 30 minutes, and then stirred at 40 ° C. for 2 hours. Distilled water was used to dilute the solid content concentration of the microgel aqueous dispersion thus obtained to 15% by mass. The average particle size was 0.23 μm.

Protective layer coating solution (1)
-1.5 g of the following inorganic layered compound dispersion (1)
・ Tetramethylammonium tetrafluoroborate salt 0.04g
(Organic cationic compound described in Patent Document 6)
・ Polyvinyl alcohol 0.06g
(Pura 105 manufactured by Kuraray Co., Ltd., saponification degree 98.5 mol%, polymerization degree 500)
・ Polyvinylpyrrolidone K30 0.01g
(Made by Tokyo Chemical Industry Co., Ltd., Mw = 40,000)
・ Vinyl pyrrolidone and vinyl acetate copolymer LUVITEC VA64W
(ICP, copolymerization ratio = 6/4) 0.01 g
・ Surfactant Emarex 710 0.01g
Made by Nippon Emulsion Co., Ltd. ・ Ion-exchanged water 6.0g

Preparation of Inorganic Layered Compound Dispersion (1) 6.4 g of synthetic mica Somasif ME-100 (manufactured by Coop Chemical Co.) is added to 193.6 g of ion-exchanged water, and the average particle size (laser scattering method) is 3 μm using a homogenizer. Dispersed until. The aspect ratio of the obtained inorganic layered compound dispersed particles was 100 or more.

(Preparation of lithographic printing plate precursor 2)
A lithographic printing plate precursor 2 (for Comparative Example 2) was prepared in the same manner as the lithographic printing plate precursor 1, except that the tetramethylammonium tetrafluoroborate salt was removed from the protective layer coating solution (1).

(Preparation of lithographic printing plate precursor 3)
A lithographic printing plate precursor 3 was produced in the same manner as the lithographic printing plate precursor 1, except that the tetramethylammonium tetrafluoroborate salt of the protective layer coating solution (1) was changed to the specific compound (P-1) A.

(Preparation of lithographic printing plate precursor 4)
A lithographic printing plate precursor 4 was produced in the same manner as the lithographic printing plate precursor 1, except that the tetramethylammonium tetrafluoroborate salt of the protective layer coating solution (1) was changed to the specific compound (P-2).

(Preparation of lithographic printing plate precursor 5)
A lithographic printing plate precursor 5 was produced in the same manner as the lithographic printing plate precursor 1, except that the tetramethylammonium tetrafluoroborate salt of the protective layer coating solution (1) was changed to the specific compound (P-3).

(Preparation of lithographic printing plate precursor 6)
A lithographic printing plate precursor 6 was produced in the same manner as the lithographic printing plate precursor 1, except that the tetramethylammonium tetrafluoroborate salt in the protective layer coating solution (1) was changed to the specific compound (P-4).

(Preparation of lithographic printing plate precursor 7)
The same as lithographic printing plate precursor 1 except that the inorganic layered compound dispersion (1) and tetramethylammonium tetrafluoroborate salt in the protective layer coating liquid (1) were changed to the following organoclay complex dispersion (1) A. Thus, a lithographic printing plate precursor 7 was prepared.

Preparation of organoclay complex dispersion liquid (1) A 16.8 g of organoclay complex (1) A is added to 183.2 g of ion-exchanged water, and the average particle size (laser scattering method) is 10 μm or less using a homogenizer. Dispersed.

(Preparation of lithographic printing plate precursor 8)
Except that the inorganic layered compound dispersion (1) and tetramethylammonium tetrafluoroborate salt in the protective layer coating liquid (1) were changed to the following organoclay complex dispersion (2), the same as the planographic printing plate precursor 1 A lithographic printing plate precursor 8 was prepared.

Preparation of organoclay complex dispersion (2) Add 16.8 g of organoclay complex (2) to 183.2 g of ion-exchanged water and use an homogenizer until the average particle size (laser scattering method) is 10 μm or less. Distributed.

(Preparation of lithographic printing plate precursor 9)
Except that the inorganic layered compound dispersion (1) and tetramethylammonium tetrafluoroborate salt in the protective layer coating solution (1) were changed to the following organoclay complex dispersion (3), the same as the planographic printing plate precursor 1 A lithographic printing plate precursor 9 was prepared.

Preparation of organoclay complex dispersion (3) 17.1 g of organoclay complex (3) is added to 182.9 g of ion-exchanged water, and the average particle size (laser scattering method) is reduced to 10 μm or less using a homogenizer. Distributed.

(Preparation of planographic printing plate precursor 10)
Except that the inorganic layered compound dispersion (1) and the tetramethylammonium tetrafluoroborate salt in the protective layer coating liquid (1) were changed to the following organoclay complex dispersion (4), the same as the planographic printing plate precursor 1 A lithographic printing plate precursor 10 was prepared.

Preparation of organoclay complex dispersion (4) Add 16.4 g of organoclay complex (4) to 183.6 g of ion-exchanged water and use an homogenizer until the average particle size (laser scattering method) is 10 μm or less. Distributed.

(Evaluation of lithographic printing plate precursor and protective layer coating solution)
The obtained lithographic printing plate precursor and protective layer coating solution were evaluated as follows.
The results are shown in Table 4.

<Stability of protective layer coating solution>
When the protective layer coating solution used in the preparation of the above lithographic printing plate precursors 1 to 10 is placed in a test tube having a diameter of 2 cm so as to have a depth of 10 cm after completion of the preparation, the inorganic fine particle dispersion liquid settles. The protective layer coating solution was separated into an upper transparent portion and a lower portion that was clouded by inorganic fine particles. The time taken for the upper transparent part to reach 1 cm was measured and evaluated as the protective layer coating solution stability. The longer the time, the higher the stability.

<On-press developability>
The resulting lithographic printing plate precursor was exposed with a Trend setter 3244VX manufactured by Creo equipped with a water-cooled 40 W infrared semiconductor laser under the conditions of an output of 9 W, an outer drum rotating speed of 210 rpm, and a resolution of 2400 dpi. The obtained exposed original plate was attached to a cylinder of a printing machine SOR-M manufactured by Heidelberg without developing. Dampening water and ink using dampening water (CDS803 manufactured by Tokyo Ink Co., Ltd. diluted 50 times with tap water) and TRANS-G (N) black ink (manufactured by Dainippon Ink & Chemicals, Inc.) Was started at a printing speed of 6000 sheets per hour.
The number of print sheets required until the on-press development on the printing press of the unexposed portion of the image recording layer was completed and no ink was transferred to the print paper was measured as on-press developability. When any lithographic printing plate precursor was used, a printed matter having no stain on the non-image area was obtained within 100 sheets.

<Ink fillability>
After printing starts, ink gradually adheres to the image area of the lithographic printing plate, and as a result, the ink density on the paper gradually increases. The number of printed sheets when the ink density reached the standard printed matter density was measured as the ink fillability.

<Print durability>
If the printing is further continued after ink deposition, the image recording layer gradually wears. Since the wear of the image recording layer has progressed and the ink receptivity has decreased, the ink density on the printing paper begins to decrease. Printing durability was evaluated by the number of printed sheets when the ink density (reflection density) was reduced by 0.1 from the start of printing.

  As can be seen from Table 4 above, when the lithographic printing plate precursor of the present invention is used, high ink setting properties can be obtained while maintaining on-press developability and printing durability, and the stability of the coating solution for the protective layer is also high. can get.

[Examples 9 to 20 and Comparative Examples 3 to 5]

(Preparation of lithographic printing plate precursor 11)
The undercoat liquid (1) was applied to the support so that the dry coating amount was 6 mg / m ² to prepare a support having an undercoat layer.
An image recording layer coating liquid (2) having the following composition is bar-coated on the support on which the undercoat layer has been formed, and then oven-dried at 100 ° C. for 60 seconds to form an image recording layer having a dry coating amount of 1.0 g / m ^2. Formed. Subsequently, a protective layer coating solution (2) having the following composition is bar-coated on the image recording layer and oven-dried at 120 ° C. for 60 seconds to form a protective layer having a dry coating amount of 0.160 g / m ^2. A lithographic printing plate precursor 11 (for Comparative Example 3) was obtained.
The image recording layer coating solution (2) was obtained by mixing the following photosensitive solution and microgel solution immediately before coating and stirring.

<Photosensitive solution>
0.177 g of the binder polymer (1)
Polymerization initiator I-28 The following structure 0.142g
Infrared absorber (2) 0.0308 g of the following structure
Polymerizable compound (Aronix M-215 (manufactured by Toa Gosei Co., Ltd.)) 0.319 g
Specific polymer (11) (Reduced viscosity 40.7CSt / g / ml) 0.035g of the following structure
(Ammonium group-containing polymer described in Patent Document 7)
Fluorosurfactant (1) 0.004g
Ionic surfactant 0.125g
(Pionine A-24-EA (Takemoto Yushi Co., Ltd., 40% by mass aqueous solution)
2-butanone 2.554g
1-methoxy-2-propanol 7.023 g

<Microgel solution>
Microgel aqueous dispersion (2) 1.800 g
1.678 g of water

<Synthesis of aqueous microgel dispersion (2)>
As an oil phase component, trimethylolpropane and xylene diisocyanate adduct (Mitsui Chemicals, Takenate D-110N, 75% by mass ethyl acetate solution) 10.0 g, and Aronix M-215 (Toagosei Co., Ltd.) as a polymerizable compound 6.00 g of Pionine A-41C (manufactured by Takemoto Yushi Co., Ltd.) was dissolved in 16.67 g of ethyl acetate. As an aqueous phase component, 37.5 g of a 4 mass% aqueous solution of polyvinyl alcohol (PVA-205 manufactured by Kuraray Co., Ltd.) was prepared. The oil phase component and the aqueous phase component were mixed and emulsified for 10 minutes at 12,000 rpm using a homogenizer. The obtained emulsion was added to 25 g of distilled water, stirred at room temperature for 30 minutes, and then stirred at 40 ° C. for 2 hours. The microgel dispersion thus obtained was diluted with distilled water so that the solid content concentration was 21% by mass to obtain a microgel dispersion (2). The average particle size was 0.23 μm.

<Protective layer coating solution (2)>
-1.5 g of the following inorganic layered compound dispersion (2)
・ Polyvinyl alcohol 0.06g
(PVA105, manufactured by Kuraray Co., Ltd., saponification degree 98.5 mol%, polymerization degree 500)
・ Polyvinylpyrrolidone 0.01g
(Polyvinylpyrrolidone K30, manufactured by Tokyo Chemical Industry Co., Ltd., Mw = 40,000)
・ Vinyl pyrrolidone / vinyl acetate copolymer 0.01g
(LUVITEC VA64W, manufactured by ISP, copolymerization ratio = 6/4)
・ Nonionic surfactant 0.013g
(Emalex 710, manufactured by Nippon Emulsion Co., Ltd.)
・ Ion-exchanged water 6.0g

<Preparation of inorganic layered compound dispersion (2)>
Synthetic mica Somasif ME-100 (manufactured by Coop Chemical Co., Ltd.) is added at a ratio of 6.4 g to 193.6 g of ion-exchanged water, and the average particle diameter (laser scattering method) is 3 μm using a homogenizer. Dispersed. The aspect ratio of the obtained dispersed inorganic particles was 100 or more.

(Preparation of lithographic printing plate precursor 12)
The lithographic printing plate except that the specific polymer (11) in the photosensitive solution is changed to the following specific polymer (2) (ammonium group-containing polymer described in Patent Document 7, reduced viscosity 25.5 CSt / g / ml) A lithographic printing plate precursor 12 (for Comparative Example 4) was produced in the same manner as the precursor 11.

(Preparation of lithographic printing plate precursor 13)
The lithographic printing plate precursor 13 (for Comparative Example 5) is the same as the lithographic printing plate precursor 11 except that the specific polymer (11) in the photosensitive solution is added (0.035 g) to the protective layer coating solution (2). Was made.

(Preparation of lithographic printing plate precursors 14 to 17)
The lithographic printing plate precursors 14 to 17 are produced in the same manner as the lithographic printing plate precursor 11 except that the specific polymer (11) in the photosensitive solution is changed to the specific compounds (P-5) to (P-8), respectively. did.

(Preparation of lithographic printing plate precursors 18 to 21)
The lithographic printing plate precursors 18 to 21 were prepared in the same manner as the lithographic printing plate precursor 13 except that the specific polymer (11) in the photosensitive solution was changed to the specific compounds (P-5) to (P-8). .

(Preparation of lithographic printing plate precursors 22 to 25)
The specific polymer (11) in the photosensitive solution was removed, and the layered compound dispersion (2) in the protective layer coating solution (2) was changed to the following organoclay complex dispersions (5) to (8). The lithographic printing plate precursors 22 to 25 were prepared in the same manner as the lithographic printing plate precursor 11.

Preparation of organoclay complex dispersion (5) Add 17.0 g of organoclay complex (5) to 183.0 g of ion-exchanged water, and use a homogenizer until the average particle size (laser scattering method) is 10 μm or less. Distributed.

Preparation of organoclay complex dispersion (6) Add 17.3 g of organoclay complex (6) to 182.7 g of ion-exchanged water and use a homogenizer until the average particle size (laser scattering method) is 10 μm or less. Distributed.

Preparation of organoclay complex dispersion (7) 16.2 g of organoclay complex (7) is added to 183.8 g of ion-exchanged water, and the average particle size (laser scattering method) is reduced to 10 μm or less using a homogenizer. Distributed.

Preparation of organoclay complex dispersion (8) Add 17.1 g of organoclay complex (8) to 182.9 g of ion-exchanged water and use an homogenizer until the average particle size (laser scattering method) is 10 μm or less. Distributed.

(Evaluation of lithographic printing plate precursor and protective layer coating solution)

<Stability of protective layer coating solution>
The protective layer coating solution used for the production of the lithographic printing plate precursors 11 to 25 was evaluated by the method described above. The results are shown in Table 5.

<Evaluation of on-press developability>
After exposure on a Trend setter 3244VX manufactured by Creo with a water-cooled 40W infrared semiconductor laser under the conditions of an output of 11.7 W, an outer drum rotation speed of 250 rpm, and a resolution of 2400 dpi, the exposed lithographic printing plate precursor is not developed and processed by Heidelberg. Attached to the cylinder of a printing machine SOR-M manufactured by the company, dampening water (EU-3 (etch solution manufactured by FUJIFILM Corporation) / water / isopropyl alcohol = 1/89/10 (volume ratio)) and TRANS-G ( N) Using black ink (manufactured by Dainippon Ink & Chemicals, Inc.), after supplying dampening water and ink, printing was performed at a printing speed of 6,000 sheets per hour. At this time, the number of print sheets required until the ink was not transferred to the unexposed portion (non-image portion) of the image recording layer was evaluated as on-press developability. The smaller the number, the better the on-press developability. The results are shown in Table 5.

<Evaluation of ink fillability>
Ink density on the printing paper is reduced as printing is performed using the lithographic printing plate precursor exposed in the same way as on-press developability evaluation, and the ink receptivity of the image recording layer gradually decreases as the number of printed sheets increases. Decreases. The number of printed sheets when the ink density (reflection density) was decreased by 0.01 from the start of printing was evaluated as the inking property. It is evaluated that the larger the number, the better the inking property. The results are shown in Table 5.

<Evaluation of printing durability>
Printing is performed using the exposed lithographic printing plate precursor in the same manner as on-machine developability evaluation, and further printing is continued.If the number of printed sheets is increased, the image recording layer gradually wears and the ink acceptability decreases. Ink density in printing paper decreases. Printing durability was evaluated by the number of printed sheets when the ink density (reflection density) was reduced by 0.1 from the start of printing. The larger the number of sheets, the better the printing durability. The results are shown in Table 5.

  As can be seen from Table 5, the lithographic printing plate precursor according to the present invention has the same printing durability as that of the comparative example and is excellent in the stability of the protective layer coating solution, the developability and the inking property.

[Examples 21 to 28]

(Preparation of planographic printing plate precursors 26 to 33)
(1) Production of support (2) In order to remove rolling oil on the surface of an aluminum plate (material JIS A 1050) having a thickness of 0.3 mm, degreasing is carried out at 50 ° C. for 30 seconds using a 10 mass% sodium aluminate aqueous solution. After the treatment, the surface of the aluminum plate was grained using ^three bundled nylon brushes having a bristle diameter of 0.3 mm and a pumice-water suspension having a median diameter of 25 μm (specific gravity: 1.1 g / cm ³ ). Washed well with. This plate was etched by being immersed in a 25 mass% sodium hydroxide aqueous solution at 45 ° C for 9 seconds, washed with water, further immersed in 20 mass% nitric acid at 60 ° C for 20 seconds, and washed with water. The etching amount of the grained surface at this time was about 3 g / m ² .
Next, an electrochemical roughening treatment was performed continuously using an alternating voltage of 60 Hz. The electrolytic solution at this time was a 1% by mass nitric acid aqueous solution (containing 0.5% by mass of aluminum ions) and a liquid temperature of 50 ° C. The AC power source waveform is electrochemical roughening treatment using a trapezoidal rectangular wave alternating current with a time ratio TP of 0.8 msec until the current value reaches a peak from zero, a duty ratio of 1: 1, and a trapezoidal rectangular wave alternating current. Went. Ferrite was used for the auxiliary anode. The current density was 30 A / dm ² at the peak current value, and 5% of the current flowing from the power source was shunted to the auxiliary anode. The amount of electricity in nitric acid electrolysis was 175 C / dm ² when the aluminum plate was the anode. Then, water washing by spraying was performed.
Subsequently, nitric acid electrolysis was performed with an aqueous solution of 0.5% by mass of hydrochloric acid (containing 0.5% by mass of aluminum ions) and an electrolytic solution having a liquid temperature of 50 ° C. under the condition of an electric quantity of 50 C / dm ² when the aluminum plate was the anode. In the same manner as above, an electrochemical surface roughening treatment was performed, followed by washing with water by spraying.
Next, a 2.5 g / m ² direct current anodic oxide film having a current density of 15 A / dm ² was provided on the plate as a 15% by weight sulfuric acid aqueous solution (containing 0.5% by weight of aluminum ions) as an electrolyte, followed by washing with water. And dried to prepare a support (1).
Thereafter, in order to ensure the hydrophilicity of the non-image area, the support (1) was subjected to a silicate treatment at 60 ° C. for 10 seconds using an aqueous 2.5 mass% No. 3 sodium silicate solution, and then washed with water for support. Body (2) was obtained. The adhesion amount of Si was 10 mg / m ² . The centerline average roughness (Ra) of this substrate was measured using a needle having a diameter of 2 μm and found to be 0.51 μm.

(2) Formation of undercoat layer Next, the following undercoat layer coating solution (2) is applied onto the support (2) so that the dry coating amount is 20 mg / m ² , and used in the following experiments. A support having a layer was prepared.

<Coating liquid for undercoat layer (2)>
-Undercoat layer compound (2) having the following structure: 0.18 g
・ Hydroxyethyliminodiacetic acid 0.10g
・ Methanol 55.24g
・ Water 6.15g

(3) Formation of image recording layer The image recording layer coating solution (3) having the following composition was bar coated on the undercoat layer formed as described above, and then oven-dried at 100 ° C for 60 seconds to obtain a dry coating amount. An image recording layer of 1.0 g / m ² was formed.
The image recording layer coating solution (3) was obtained by mixing and stirring the following photosensitive solution (2) and the following microgel solution immediately before coating.

<Photosensitive solution (2)>
-Binder polymer (2) [the following structure] 0.240 g
Infrared absorber (2) [above structure] 0.030 g
・ Polymerization initiator (1) [the following structure] 0.162 g
Polymerizable compound tris (acryloyloxyethyl) isocyanurate (NK ester A-9300, manufactured by Shin-Nakamura Chemical Co., Ltd.) 0.192 g
・ Low molecular weight hydrophilic compound Tris (2-hydroxyethyl) isocyanurate 0.062g
・ Low molecular weight hydrophilic compound (1) [the following structure] 0.050 g
-Sensitizing agent Phosphonium compound (1) [the following structure] 0.055 g
・ Sensitizer Benzyl-dimethyl-octylammonium ・ PF ₆ salt 0.018g
-Specific compounds listed in Table 6 0.035 g
-Fluorine-based surfactant (1) 0.008 g
・ 2-butanone 1.091g
・ 1-methoxy-2-propanol 8.609g

<Microgel solution>
-Microgel aqueous dispersion (3) 2.640 g
・ Distilled water 2.425g

  The structures of the binder polymer (2), the polymerization initiator (1), the phosphonium compound (1), and the low molecular weight hydrophilic compound (1) are as shown below.

-Synthesis of aqueous microgel dispersion (3)-
As an oil phase component, trimethylolpropane and xylene diisocyanate adduct (Mitsui Chemical Polyurethane Co., Ltd., Takenate D-110N) 10 g, pentaerythritol triacrylate (Nippon Kayaku Co., Ltd., SR444) 3.15 g, And 0.1 g of Pionein A-41C (manufactured by Takemoto Yushi Co., Ltd.) was dissolved in 17 g of ethyl acetate. As an aqueous phase component, 40 g of a 4% by mass aqueous solution of polyvinyl alcohol (PVA-205 manufactured by Kuraray Co., Ltd.) was prepared. The oil phase component and the aqueous phase component were mixed and emulsified for 10 minutes at 12,000 rpm using a homogenizer. The obtained emulsion was added to 25 g of distilled water, stirred at room temperature for 30 minutes, and then stirred at 50 ° C. for 3 hours. The microgel solution thus obtained was diluted with distilled water to a solid content concentration of 15% by mass, and this was used as a microgel aqueous dispersion (3). When the average particle size of the microgel was measured by a light scattering method, the average particle size was 0.2 μm.

(3) Formation of Protective Layer After the bar coating of the protective layer coating solution (3) having the following composition was further applied on the image recording layer, it was oven-dried at 120 ° C. for 60 seconds, and the dry coating amount was 0.15 g / m ^2. A lithographic printing plate precursor 26 to 33 was obtained.

<Protective layer coating solution (3)>
・ 1.5 g of the inorganic layered compound dispersion (2)
-Polyvinyl alcohol (Nippon Synthetic Chemical Industry Co., Ltd. CKS50, sulfonic acid modification,
Saponification degree 99 mol% or more, polymerization degree 300) 6% by mass aqueous solution 0.55 g
・ Polyvinyl alcohol (PVA-405 manufactured by Kuraray Co., Ltd.)
Degree of saponification 81.5 mol%, degree of polymerization 500) 6% by weight aqueous solution 0.03 g
・ Nippon Emulsion Co., Ltd. surfactant (Emalex 710) 1% by weight aqueous solution 0.86g
・ Ion-exchanged water 6.0g

  The resulting lithographic printing plate precursor was evaluated in the same manner as in Example 1 for on-press developability, printing durability, and ink deposition. The results are shown in Table 6 below.

  As shown in Table 6, the lithographic printing plate precursor of the present invention has good on-press developability, printing durability, and ink setting property, but the ink setting property when the specific compound is Mw 500 or less. When it is Mw 50000 or more, developability is slightly lowered.

[Examples 29 to 36]

(Preparation of lithographic printing plate precursors 34 to 41)
The planographic printing plate precursors 34 to 34 are the same as the planographic printing plate precursor 26 except that the specific compound is removed from the photosensitive solution (2) and the protective layer coating solution (3) is changed to the following protective layer coating solution (4). 41 was produced.

<Protective layer coating solution (4)>
・ 1.5 g of organoclay composites listed in Table 7
・ Ion-exchanged water 6.0g

(Evaluation of lithographic printing plate precursor and protective layer coating solution)
The obtained lithographic printing plate precursor was evaluated in the same manner as in Example 1 for the protective layer coating solution stability, on-press developability, printing durability, and ink landing property. The results are shown in Table 7 below.

  As shown in Table 7, the lithographic printing plate precursor of the present invention is good in all of the protective layer coating solution stability, on-press developability, printing durability, and ink landing property. When the Mw is 500 or less, the stability of the protective layer coating solution and the ink deposition property are slightly lowered, and when the Mw is 50000 or more, the developability and the printing durability are slightly lowered.

[Examples 37 to 40]

(Preparation of lithographic printing plate precursors 42 to 45)
The following image recording layer coating solution (4) was applied to a brush-polished and phosphoric acid-anodized polyacrylic acid post-treated aluminum substrate using a winding rod and then set at 90 ° C. And dried in a Ranar conveyor furnace for about 90 seconds. The dry coating amount obtained was 1.5 g / m ² .

<Image recording layer coating solution (4)>
・ Urethane acrylate 2.48g
・ Copolymer 1 13.53 g
・ Copolymer 2 3.97 g
・ Infrared absorber (3) [the following structure] 0.13 g
・ Polymerization initiator Irgacure250 (Ciba Specialty Chemicals) 0.42g
・ Mercapto-3-triazole 0.18g
・ Byk336 (Byk Chimie) 0.60g
・ KlucelM (Hercules) 3.31g
・ Propanol 61.97g
・ Ion-exchanged water 13.41g

The compounds in the above formulation are as follows.
* Urethane acrylate: 80% by weight 2-butanone solution of urethane acrylate obtained by reaction of DESMODUR N100 with hydroxyethyl acrylate and pentaerythritol triacrylate * Copolymer 1: a mixture of 54 g of propanol and 16 g of deionized water. Charged into a 250 mL flask, which was heated to 70 ° C., purged with a steady stream of nitrogen gas, and stirred with a mechanical stirrer. A mixture of 54 g propanol, 16 g deionized water, 10 g PEGMA, 4.5 g styrene, 40.5 g acrylonitrile, and 0.32 g VAZO-64 was prepared in a separate beaker, which was then added for 30 minutes. Over a 250 mL flask. After 2.5 hours, 0.16 g of VAZO-64 was added to the reaction mixture. The polymerization reaction lasted for another 2 hours. The resulting polymer solution contained 21% solids by weight of copolymer 1.
* Copolymer 2: 2-butanone (384.1 g) and 8.5 g of PEGMA were charged into a 1 L four neck flask under a nitrogen atmosphere and heated to 80 ° C. A premix of allyl methacrylate (38.0 g) and VAZO-64 (0.3 g) was added at 80 ° C. over 90 minutes. After the addition was complete, an additional 0.13 g of VAZO-64 was added. Thereafter, 0.13 g of VAZO-64 was added twice more. The polymer conversion based on percent nonvolatiles was> 98%.
* PEGMA: Sigma-Aldrich Corp. Poly (ethylene glycol) methyl ether methacrylate available from (St. Louis, Missouri); average Mn-2080 as a 50 wt% aqueous solution.
* VAZO-64: E.E. I. du Pont de Nemours and Co. 2,2′-Azobisisobutyronitrile available from (Wilmington, Delaware).
* Infrared absorber (3): The following structure

* IRGACURE 250: 75 wt% propylene carbonate solution of (4-methylphenyl) [4- (2-methylpropyl) phenyl] iodonium hexafluorophosphate available from Ciba Specialty Chemicals (Tarrytown, New York) * Byk 336: Byk-Chemie USA Inc. (Wallingford, Connecticut), a modified dimethylpolysiloxane copolymer in a 25 wt% xylene / methoxypropyl acetate solution * KLUCEL M: Hercules Inc. , Aqualon Division (Wilmington, Delaware), 2% by weight aqueous solution of hydroxypropylcellulose (viscosity: 5.000 mPa · s)

A protective layer coating solution (5) having the following composition was bar coated on the obtained image recording layer, and then oven-dried at 120 ° C. for 60 seconds to form a protective layer having a dry coating amount of 0.35 g / m ^2. This was formed to obtain a lithographic printing plate precursor.

<Protective layer coating solution (5)>
・ 1.5 g of organoclay composite dispersion described in Table 8
-Polyvinyl alcohol (Nippon Synthetic Chemical Industry Co., Ltd. CKS50, sulfonic acid modification,
Saponification degree 99 mol% or more, polymerization degree 300) 6% by mass aqueous solution 0.55 g
・ Polyvinyl alcohol (PVA-405 manufactured by Kuraray Co., Ltd.)
Degree of saponification 81.5 mol%, degree of polymerization 500) 6% by weight aqueous solution 0.03 g
・ Nippon Emulsion Co., Ltd. surfactant (Emalex 710) 1% by weight aqueous solution 0.86g
・ Ion-exchanged water 6.0g

(Evaluation of lithographic printing plate precursor and protective layer coating solution)
The obtained lithographic printing plate precursor was evaluated in the same manner as in Example 1 for the protective layer coating solution stability, on-press developability, printing durability, and ink landing property. The results are shown in Table 8 below.

[Examples 41 to 45]

(Preparation of lithographic printing plate precursors 46-50)
The following image recording layer coating solution (5) was applied to a brush-polished and phosphoric acid-anodized polyacrylic acid post-treated aluminum substrate using a winding rod and then set at 90 ° C. And dried in a Ranar conveyor furnace for about 90 seconds. The dry coating mass obtained was 0.88 g / m ² .

Image recording layer coating solution (5)
・ Polymer A 3.56g
・ Oligomer A 1.21 g
・ Infrared absorber (4) 0.16g
・ Mercapto-3-triazole 0.11g
・ SR-399 2.43g
・ Klucel E 3.89g
・ NaBPh ₄ 0.08g
・ Byk336 0.35g
・ Blue 63 1.79g
・ 2,4-Dihydroxybenzophenone 0.09g
・ Irganox 1035 0.19g
・ Irgacure 250 (above) 0.37g
・ Propanol 63.05 g
・ Ion exchange water 5.38g
・ 2-butanone 17.34g

The compounds in the above formulation are as follows.
* Oligomer A: The above urethane acrylate.
* Polymer A: PEGMA / styrene / acrylonitrile = 10/20/70 (mass ratio) copolymer (24 mass% propanol solution).
* Infrared absorber (4): (Structure below)

* SR-399: Dipentaerythritol pentaacrylate (manufactured by Sartomer) (used as a 40% by weight 2-butanone solution).
* Klucel E: 5% by mass aqueous solution of hydroxypropylcellulose (Hercules)
* Blue 63: The following structure

* Irganox 1035: Thiodiethylene bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate 5 mass% 2-butanone solution (Ciba Specialty Chemicals).

On the obtained image recording layer, the protective layer coating liquid (5) (however, the organic clay composite aqueous dispersion used is the one described in Table 9) was bar coated, and then 120 ° C., 60 seconds. And a protective layer having a dry coating amount of 0.35 g / m ² was formed to obtain a lithographic printing plate precursor.

(Evaluation of lithographic printing plate precursor and protective layer coating solution)
The obtained lithographic printing plate precursor was evaluated in the same manner as in Example 1 for the protective layer coating solution stability, on-press developability, printing durability, and ink landing property. The results are shown in Table 9 below.

[Examples 46 to 52 and Comparative Examples 6 to 7]

(Preparation of lithographic printing plate precursors 51-59)
Example 1 except that the image recording layer coating liquid (1) was changed to the following image recording layer coating liquid (6) and the protective layer coating liquid (1) was changed to the following protective layer coating liquid (6). Similarly, lithographic printing plate precursors 51 to 59 were prepared.

Image recording layer coating solution (6)
-The following binder polymer (3) (Mw: 80,000) 0.34 g
・ The following polymerizable compound (2) 0.68 g
(PLEX6661-O, manufactured by Degussa Japan)
・ The following sensitizing dye (1) 0.06 g
・ The following polymerization initiator (2) 0.18 g
・ The following chain transfer agent (1) 0.02 g
・ 0.40 g of ε-phthalocyanine pigment dispersion
(Pigment: 15 parts by mass, dispersant (allyl methacrylate / methacrylic acid copolymer (Mw: 60,000, copolymer molar ratio: 83/17)):
(10 parts by mass, cyclohexanone: 15 parts by mass)
-Thermal polymerization inhibitor N-nitrosophenylhydroxylamine aluminum salt 0.01 g
-Fluorine-based surfactant (1) 0.001 g
・ Polyoxyethylene-polyoxypropylene condensate 0.02g
(Pluronic L44, manufactured by ADEKA Corporation)
・ Dispersion of yellow pigment 0.04g
(Yellow pigment Novoperm Yellow H2G (manufactured by Clariant): 15 parts by mass,
Dispersant (allyl methacrylate / methacrylic acid copolymer (Mw: 60,000,
Copolymerization molar ratio 83/17)): 10 parts by mass, cyclohexanone: 15 parts by mass)
・ 3.5 g of 1-methoxy-2-propanol
・ 2-butanone 8.0g

<Protective layer coating solution (6)>
・ 1.5 g of organoclay composite dispersion described in Table 10
-Polyvinyl alcohol (Nippon Synthetic Chemical Industry Co., Ltd. CKS50, sulfonic acid modification,
Saponification degree 99 mol% or more, polymerization degree 300) 6% by mass aqueous solution 0.55 g
・ Polyvinyl alcohol (PVA-405 manufactured by Kuraray Co., Ltd.)
Degree of saponification 81.5 mol%, degree of polymerization 500) 6% by weight aqueous solution 0.03 g
・ Nippon Emulsion Co., Ltd. surfactant (Emalex 710) 1% by weight aqueous solution 0.86g
・ Ion-exchanged water 6.0g

(Exposure, development and printing of planographic printing plate precursor)
Each lithographic printing plate precursor shown in Table 10 was obtained from FUJIFILM Electronic Imaging Ltd. Image exposure was performed with a Violet semiconductor laser plate setter Vx9600 (InGaN-based semiconductor laser (with an emission wavelength of 405 nm ± 10 nm / output 30 mW) mounted) manufactured by (FFEI). Image exposure was performed at a plate surface exposure of 0.05 mJ / cm ² with a resolution of 2,438 dpi and an FM screen (TAFFETA 20) manufactured by FUJIFILM Corporation so that the dot area ratio was 50%.
Next, after preheating at 100 ° C. for 30 seconds, the following developing solution 1 was used, and development processing was performed with an automatic developing processor having a structure as shown in FIG. The automatic processor has one brush roll with an outer diameter of 50 mm in which fibers made of polybutylene terephthalate (hair diameter 200 μm, hair length 17 mm) are implanted, and rotates 200 times per minute in the same direction as the conveying direction ( The peripheral speed of the brush tip was 0.52 m / sec). The temperature of the developer was 30 ° C. The planographic printing plate precursor was transported at a transport speed of 100 cm / min. After the development processing, drying was performed in a drying section. The drying temperature was 80 ° C.

<Developer 1>
・ Sodium carbonate 13.0g
・ 7.0g sodium bicarbonate
・ New Coal B13 (Nippon Emulsifier Co., Ltd., polyoxyethylene β-naphthyl ether (oxyethylene average number n = 13) 50.0 g
・ Primary ammonium phosphate 2.0g
・ 2-Bromo-2-nitropropane-1,3-diol 0.01 g
・ 0.01 g of 2-methyl-4-isothiazolin-3-one
・ Trisodium citrate 15.0g
・ Distilled water 913.98 g
(PH of developer 1: 9.8)

  The obtained lithographic printing plate is attached to a printing machine SOR-M manufactured by Heidelberg, and fountain solution (EU-3 (etch solution manufactured by FUJIFILM Corporation) / water / isopropyl alcohol = 1/89/10 (volume ratio). )) And TRANS-G (N) black ink (manufactured by Dainippon Ink & Chemicals, Inc.), printing was performed at a printing speed of 6000 sheets per hour.

(Evaluation of lithographic printing plate precursor and protective layer coating solution stability)
For each lithographic printing plate precursor, the protective layer coating solution stability, printing durability, ink landing property, and developability were evaluated as follows. The results are shown in Table 10.

<Stability of protective layer coating solution>
Evaluation was performed according to the method described above.

<Print durability>
As the number of printed sheets increased, the image recording layer was gradually worn out and the ink acceptance decreased, so that the ink density in the printing paper decreased. In the printing plate exposed with the same exposure amount, the printing durability was evaluated by the number of printed sheets when the ink density (reflection density) was reduced by 0.1 from the start of printing.

<Ink fillability>
Evaluation was performed according to the same method as in Example 1.

<Developability>
The above development processing was performed at various conveying speeds, and the cyan density of the non-image area of the obtained lithographic printing plate was measured with a Macbeth densitometer. The transport speed (cm / min) at which the cyan density of the non-image area became equal to the cyan density of the aluminum support was determined and defined as developability.

4 Planographic printing plate precursor (PS version)
DESCRIPTION OF SYMBOLS 6 Developing part 10 Drying part 16 Carry-in roller 20 Developing tank 22 Carrying roller 24 Brush roller 26 Squeeze roller (unloading roller)
28 Backup roller 36 Guide roller 38 Skewer roller

Claims (17)

A lithographic printing plate precursor having, on a support, an image recording layer containing a polymerization initiator and a radical polymerizable compound, and a protective layer containing an inorganic layered compound, the functional group represented by the following general formula (1) And a polymer having a structural unit represented by the following general formula (2) in at least one of the image recording layer and the protective layer.

In the formula, R _{1 to} R ₃ each independently represents an alkyl group or an aryl group having 1 to 7 carbon atoms, and any two of R _{1 to} R ₃ may form a ring, and X is N or P represents L ₁ represents a divalent linking group, Y ⁻ represents a counter anion, R ₄ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R _{5 to} R ₆ each independently Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, or R ₅ and R ₆ are connected to each other to represent —CH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ CH ₂ —, —CH ₂ CH _2. CH ₂ CH ₂ CH ₂ — or —CH ₂ CH ₂ OCH ₂ CH ₂ — is represented.   The lithographic printing plate precursor as claimed in claim 1, wherein the image recording layer contains a polymer having a functional group represented by the general formula (1) and a structural unit represented by the general formula (2).   The lithographic printing plate precursor as claimed in claim 1, wherein the protective layer contains a polymer having a functional group represented by the general formula (1) and a structural unit represented by the general formula (2).   After replacing the cation present in the inorganic layered compound with a polymer having a functional group represented by the general formula (1) and a structural unit represented by the general formula (2) to form an organoclay complex, coating with a protective layer 4. The lithographic printing plate precursor as claimed in claim 3, wherein a protective layer is formed by adding to the liquid and coating the image recording layer.   The lithographic printing plate precursor as claimed in any one of claims 1 to 4, wherein the functional group represented by the general formula (1) is present at the end of the main chain of the polymer. In the general formula (1), R ₁ and R ₂ are each independently selected from a methyl group, an ethyl group, a propyl group, a butyl group and a phenyl group, and R ₃ is a methyl group, an ethyl group, a propyl group, a butyl group, a benzyl group The lithographic printing plate precursor as claimed in claim 1, wherein the lithographic printing plate precursor is selected from a group and a phenyl group. In the general formula (2), R ₄ is selected from a hydrogen atom and a methyl group, and R ₅ and R ₆ are each independently selected from a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, and a tert-butyl group. or _{R 5} and _{R 6} are _-CH 2 _CH 2 _OCH 2 CH ₂ formed by connecting - lithographic according to any one of claims 1 to 6, characterized in that either a A printing plate master.   The lithographic printing plate precursor as claimed in any one of claims 1 to 7, wherein the inorganic layered compound is any one selected from smectite and mica.   The lithographic plate according to claim 1 or 3, wherein the protective layer further contains a water-soluble polymer other than the polymer having the functional group represented by the general formula (1) and the structural unit represented by the general formula (2). A printing plate master.   The lithographic printing according to claim 1 or 2, wherein the image recording layer further contains a polymer other than the polymer having the functional group represented by the general formula (1) and the structural unit represented by the general formula (2). Version original edition.   2. The lithographic printing plate precursor as claimed in claim 1, wherein the image recording layer further contains an infrared absorber.   After the lithographic printing plate precursor according to any one of claims 1 to 11 is imagewise exposed with a laser, it is mounted on a printing press and developed by supplying at least one of ink and fountain solution, A lithographic printing method characterized by printing.   An organoclay composite obtained by replacing a cation present in an inorganic layered compound with a polymer having a functional group represented by the general formula (1) and a structural unit represented by the general formula (2).   The organoclay composite according to claim 13, wherein the functional group represented by the general formula (1) is present at the end of the main chain of the polymer. In the general formula (1), R ₁ and R ₂ are each independently selected from a methyl group, an ethyl group, a propyl group, a butyl group and a phenyl group, and R ₃ is a methyl group, an ethyl group, a propyl group, a butyl group, The organoclay complex according to claim 13 or 14, wherein the organoclay complex is selected from a benzyl group and a phenyl group. In the general formula (2), R ₄ is selected from a hydrogen atom and a methyl group, and R ₅ and R ₆ are each independently selected from a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, and a tert-butyl group. The group according to any one of claims 13 to 15, wherein the group is -CH ₂ CH ₂ OCH ₂ CH _2- formed by linking R ₅ and R ₆ together. The organoclay composite according to Item.   The organoclay composite according to any one of claims 13 to 16, wherein the inorganic layered compound is at least one selected from smectite and mica.

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