JP2008216364A - Planographic printing original plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a planographic printing original plate excellent in hydrophilicity and its retention property of a non-image portion and plate wear owing to adhesiveness between an image portion and a support, regardless of the raw material of the support substrate. <P>SOLUTION: The planographic printing original plate has a hydrophilic layer and an image forming layer, in this order on a support, the hydrophilic layer comprising chemically bonded polymers having at least one kind of reactive group in reactive groups capable of forming direct chemical bonds to the support surface and reactive groups capable of forming chemical bonds through a structural component having a crosslinking structure with the support surface, and containing a structural unit (i) and a structural unit (ii) in general formula (1). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a lithographic printing plate precursor, and more particularly, to a lithographic printing plate precursor excellent in hydrophilicity in a non-image area and printing durability in an image area.

An aluminum support for a lithographic printing plate (hereinafter simply referred to as a “lithographic printing plate support”) used in a lithographic printing plate is roughened on an aluminum plate for the purpose of improving the printing durability of the lithographic printing plate. Manufactured by surface treatment or other surface treatment. Examples of the roughening treatment include mechanical roughening treatment, electrochemical roughening treatment (hereinafter also referred to as “electrolytic roughening treatment”), and chemical roughening treatment (chemical etching). Furthermore, a method combining these roughening treatments is known.
In a lithographic printing plate precursor, the composition of the image forming layer formed on the surface and the adhesion between the support and the image forming layer have a great influence on the printing durability. From this viewpoint, the roughening state is controlled. Thus, a technique for improving the adhesion with the image forming layer is generally employed.
Among them, by forming relatively large unevenness by mechanical surface roughening treatment and smaller unevenness by subsequent electrochemical surface roughening treatment, adhesion of image forming layer, printing durability and aluminum support A technique for improving the hydrophilicity of the body surface is useful.
As a mechanical surface roughening treatment, a method of spraying an abrasive slurry between a rotating nylon brush and an aluminum plate is generally known. Further, as an electrolytic surface roughening treatment, a method of performing alternating current or direct current in a hydrochloric acid or nitric acid electrolytic solution is known.
As the above lithographic printing plate aluminum support (hereinafter simply referred to as “lithographic printing plate support”), since it is easy to roughen the surface, the pure aluminum plate or the aluminum purity is 99.5% or more. An alloy plate containing a trace amount of foreign elements (for example, silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, titanium, etc.) is used. As described above, in the prior art, it is common to use a high-purity aluminum material as a raw material for a lithographic printing plate support.

On the other hand, aluminum materials having an aluminum purity of 95 to 99.4% by mass, such as aluminum bullion made from used aluminum beverage cans (hereinafter sometimes referred to as UBC), are known as inexpensive materials. ing. If the UBC material can be used as a support for a lithographic printing plate, it has the possibility of producing a product at a low cost and is a material that can reduce the burden on the environment because of its high recyclability.
A method for producing a support for a lithographic printing plate precursor by subjecting a UCB aluminum plate to a specific surface-roughening treatment is disclosed. (For example, refer to Patent Document 1). In this manufacturing method, a mechanical surface roughening process is carried out with a nylon brush and an abrasive, but the processability of the surface roughening decreases due to the influence of mixed impurities, and it is used as a support for a lithographic printing plate. A suitable surface may not be obtained.
Furthermore, when electrochemical surface roughening is performed, at the locations where the impurity metal is unevenly distributed, the alloy portion of the impurities and aluminum is peeled off to form an opening, making it difficult to perform fine and uniform surface roughening. there were.

  Regarding the hydrophilicity of the support surface, for example, it was formed by hydrolysis and polycondensation of a metal alkoxide having a hydrophilic graft chain on the substrate surface and selected from Si, Ti, Zr, and Al. A support for a lithographic printing plate comprising a crosslinked structure is disclosed (for example, see Patent Document 2). The patent document describes that JIS 1050 high-purity aluminum is effective for surface hydrophilization when used as a support. However, such surface treatment technology has been conventionally studied only for highly homogenous aluminum substrates, and is applied to low-purity aluminum such as UBC to produce a support for a lithographic printing plate precursor and The effect of impurities contained in low-purity aluminum is difficult to predict from the prior art because the effect is not known at all.

2. Description of the Related Art In recent years, lithographic printing plate precursors for direct printing plates in which plate making is performed directly from digital data using a laser having an emission wavelength from the near infrared to the infrared region as a light source have been widely used. This is attracting attention because it is superior in handleability and storage stability under white light compared to a conventional image forming layer that is made by ultraviolet exposure.
In a known positive lithographic printing plate precursor for infrared laser for direct plate making, a novolak resin or the like is used as an alkaline aqueous solution-soluble resin. Among them, substances that generate heat by absorbing light and positive photosensitive compounds such as various onium salts and quinonediazide compounds were added to an aqueous alkali-soluble resin having a phenolic hydroxyl group such as a novolak resin. The one having an image forming layer is disclosed as an excellent positive lithographic printing plate precursor for infrared laser from which a high-quality image can be obtained (for example, see Patent Document 3).
In addition, the negative type lithographic printing plate precursor includes a polymerization initiator, a polymerizable compound and a substance that generates light by absorbing light, a radical polymerization type image forming layer in which an exposed region is polymerized and cured, And a non-processing type image forming layer that does not require a wet development process in which an exposed area is fused to form a hydrophobic area.

In such a lithographic printing plate precursor for infrared laser, heat generated by infrared laser exposure is used as energy for image formation. For example, when an aluminum substrate is used, thermal energy diffuses to the support. Alternatively, there is a problem that light used for exposure due to the photothermal conversion agent contained in the image forming layer is difficult to reach the deep part of the image forming layer efficiently, and the image forming property at the interface with the support, the image part There is still room for improvement in terms of printing durability due to adhesion between the substrate and the support, and anti-staining properties on non-image areas.
JP 2003-39846 A JP 2003-127561 A JP-A-7-285275

  The object of the present invention in consideration of the above problems is to provide both the hydrophilicity of the non-image area and its durability, and the printing durability due to the adhesion between the image area and the support, regardless of the material of the support substrate. It is to provide an excellent lithographic printing plate precursor.

  As a result of diligent research, the present inventor achieved the above object by forming a hydrophilic layer formed by chemically bonding a hydrophilic polymer having a specific reactive group and a specific side chain structure on the support surface. As a result, the present invention was completed.

That is, the present invention has the following configuration.
<1> On the support, at least one of a reactive group that can be chemically bonded directly to the surface of the support and a reactive group that can be chemically bonded to the support surface through a component having a crosslinked structure. A hydrophilic layer formed by chemically bonding a polymer containing the structural unit (i) and the structural unit (ii) in the following general formula (1), and an image forming layer in this order A lithographic printing plate precursor characterized by that.

In General Formula (1), R ¹ , R ² , R ³ , and R ⁴ each independently represent a hydrogen atom or a substituent having 1 to 30 carbon atoms, m represents 0, 1 or 2, and L ¹ Represents a single bond or an organic linking group, and Y ¹ has at least a structure selected from —CO—NH—CO—, —CO—NH—SO ₂ —, and —SO ₂ —NH—SO ₂ —. A substituent having 1 to 30 carbon atoms is represented. Here, the polymer containing the structural unit in the general formula (1) is a silane represented by the structural unit (i) at the end of a structure in which a plurality of repeating units represented by the structural unit (ii) are connected. It means a polymer compound having a coupling group.
<2> On the support, at least one of a reactive group that can be chemically bonded directly to the surface of the support and a reactive group that can be chemically bonded to the support surface through a component having a crosslinked structure. A hydrophilic layer formed by chemically bonding a polymer containing the structural unit (iii) and the structural unit (iv) in the following general formula (2), and an image forming layer in this order A lithographic printing plate precursor characterized by that.

In General Formula (2), R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ each independently represent a hydrogen atom or a substituent having 1 to 30 carbon atoms, and n is 0, 1 or 2 L ² represents a single bond or an organic linking group, and Y ² is selected from —CO—NH—CO—, —CO—NH—SO ₂ —, and —SO ₂ —NH—SO ₂ —. Represents a substituent having 1 to 30 carbon atoms and having at least the following structure.
<3> The lithographic printing plate precursor as described in <1> or <2>, wherein the support is an aluminum support.
<4> The lithographic printing plate precursor as described in <3>, wherein the aluminum constituting the aluminum support has a purity of 99.4 to 95% by mass.
<5> The lithographic printing plate precursor as described in <1> or <2>, wherein the support is a plastic film support.
<6> The constituent component having a crosslinked structure has a crosslinked structure formed by hydrolysis and condensation polymerization of an alkoxide compound containing an element selected from Si, Ti, Zr, and Al. <1 > The lithographic printing plate precursor as described in any one of <5>.

<7> The lithographic printing plate precursor as described in any one of <1> to <6>, wherein the image forming layer is recordable with an infrared laser.
<8> The lithographic printing plate precursor as described in <7>, wherein the image forming layer contains an infrared absorber.
<9> The lithographic printing plate precursor as described in any one of <1> to <8>, wherein the image forming layer has a laminated structure of two or more layers.
<10> The lithographic printing plate precursor as described in any one of <1> to <9>, wherein the image forming layer is a positive image forming layer containing a novolak resin.
<11> The <10>, wherein the positive type image forming layer contains an alkali-soluble resin containing 50% by mass or more of a novolak resin with respect to the total alkali-soluble resin, and a sulfonium compound or an ammonium compound. The lithographic printing plate precursor described.

Although the mechanism of action of the present invention is not clear, the polymer having a specific substituent in the side chain that forms the hydrophilic layer is chemically bonded directly to the surface of the aluminum substrate in the molecule, or has a crosslinked structure. Since the polymer has a reactive group that can be chemically bonded via a constituent component, the polymer is firmly bonded to a functional group such as -Al ³⁺ or -OH present on the surface of the aluminum base. It is presumed that the adhesion between the hydrophilic layer formed by the substrate and the support and the durability thereof are good.
Furthermore, it binds to the support derived from a specific substituent (—CO—NH—CO—, —CO—NH—SO ₂ —, or —SO ₂ —NH—SO ₂ —) present in the side chain. In the preferred embodiment of the present invention, it is considered that the obtained polymer has excellent hydrophilicity, and even when any support is used, excellent hydrophilicity can be imparted to the surface. By using a hydrophilic polymer having a reactive group at the end, this polymer is firmly fixed to the support surface at one end, while the other end exists in a relatively free state, and the mobility of the polymer Therefore, it is presumed that the hydrophilicity can be further improved.
As an image forming layer of a lithographic printing plate precursor, a positive type in which an exposed portion is solubilized during development and a negative type in which an exposed portion is insoluble are known. In the present invention, either a positive type or a negative type is known. In the case of having an image forming layer, the lithographic printing plate having a positive image forming layer can be obtained because the specific hydrophilic layer in the present invention can be further improved in hydrophilicity by contact with an aqueous alkali solution. It can be particularly preferably used for the original plate.

  According to the present invention, the lithographic printing plate is excellent in both the hydrophilicity of the non-image area and its durability and the printing durability resulting from the adhesion between the image area and the support, regardless of the material of the support substrate. An original version can be provided.

[Lithographic printing plate precursor]
The lithographic printing plate precursor according to the invention has a reactive group that can be directly chemically bonded to the surface of the support on the support, or a reactive group that can be chemically bonded to the substrate surface via a component having a crosslinked structure. A hydrophilic layer formed by chemically bonding a hydrophilic polymer having at least one of the above and a specific hydrophilic functional group described in detail below, and an image forming layer in this order. .
Here, having a support, a hydrophilic layer, and an image forming layer in this order means that these layers are laminated in this order on the support, and a layer provided as necessary, for example, The existence of known layers such as a backcoat layer, an undercoat layer and an overcoat layer is not denied.

Hereinafter, these configurations will be sequentially described.
<Support>
The support used in the lithographic printing plate precursor according to the present invention is a dimensionally stable plate-like material, and is not particularly limited as long as it has necessary strength, durability, flexibility, and the like. For example, paper, paper laminated with plastic (eg, polyethylene, polypropylene, polystyrene, etc.), metal plate (eg, aluminum, zinc, copper, etc.), plastic film (eg, cellulose diacetate, cellulose triacetate, cellulose propionate) , Cellulose acetate propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, polyimide, etc.), and paper or plastic films on which the above metals are laminated or deposited Cited .
Among them, as the support, a polyester film or an aluminum plate is preferable, and among them, an aluminum plate that has good dimensional stability and is relatively inexpensive is particularly preferable.
Usually, plastic films are often inferior in surface hydrophilicity, but by forming a specific hydrophilic layer according to the present invention described below in detail on the surface, for example, a hydrophobic plastic film is used as a support. Even when it is used, it can provide excellent hydrophilicity and sustainability required for a support for a lithographic printing plate precursor. Therefore, according to the lithographic printing plate precursor of the present invention, it is possible to select a support substrate. It also has the advantage that the width is increased.

When a plastic film is used as the support substrate, the adhesion between the film substrate and the specific hydrophilic layer described later can be further improved by performing a surface treatment. As examples of the surface treatment, for example, glow discharge treatment, ultraviolet irradiation treatment, corona treatment, flame treatment, acid or alkali treatment can be used. The glow discharge treatment here may be a treatment with low-temperature plasma that occurs under a low pressure gas of 10 ^{−3 to} 20 Torr, and plasma treatment under atmospheric pressure is also preferably used. The plasma-excitable gas used for the plasma treatment may be any gas that is plasma-excited under the pressure conditions as described above, for example, argon, helium, neon, krypton, xenon, nitrogen, carbon dioxide, Examples thereof include chlorofluorocarbons such as tetrafluoromethane and mixtures thereof. Details of these are described in detail in pages 30 to 32 of the Japan Society of Invention Disclosure Technical Bulletin (Public Technical Number 2001-1745, published on March 15, 2001, Japan Institute of Invention). Note that, in the plasma treatment at atmospheric pressure which has been attracting attention in recent years, for example, irradiation energy of 20 to 500 kgy is used under 10 to 1000 keV, and more preferably irradiation energy of 20 to 300 kgy is used under 30 to 500 keV.

  A suitable aluminum plate is an alloy plate containing aluminum as a main component and containing a trace amount of foreign elements, and may be a plastic film on which aluminum is laminated or vapor-deposited. Examples of foreign elements contained in the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, and titanium. The total content of foreign elements in the alloy is preferably 5% by mass or less. Particularly suitable aluminum in the present invention is pure aluminum, but completely pure aluminum is difficult to produce in the refining technique, and may contain slightly different elements. Thus, the composition of the aluminum plate applied to the present invention is not specified, and an aluminum plate made of a publicly known material can be appropriately used. The thickness of the aluminum plate used in the present invention is about 0.1 mm to 0.6 mm, preferably 0.15 mm to 0.4 mm, and particularly preferably 0.2 mm to 0.3 mm.

<Aluminum plate>
The aluminum plate used in the present invention will be described.
The composition of the aluminum material used for the aluminum plate of the present invention may be any known one. In general, in addition to a general-purpose high-purity aluminum substrate, for example, the aluminum content is 99.4 to 95% by mass. Similarly, a low-purity aluminum substrate can be preferably used.
Therefore, as a support in the present invention, it is usually difficult to apply to a high-quality printing plate, and is obtained by rolling a UBC (Used Beverage Can) ingot in which a used aluminum beverage can is dissolved. An aluminum material or a material prepared by mixing UBC ingots with other aluminum ingots at an arbitrary ratio can also be suitably used.

Generally, the foreign elements that may be contained in the aluminum plate include, for example, silicon, iron, copper, titanium, gallium, vanadium, zinc, chromium, zirconium, barium, cobalt, etc., and the content of the foreign elements in the alloy Is 5% by mass or less.
Examples of inevitable impurities contained in the aluminum alloy include lead, nickel, tin, indium, and boron.

  The foreign elements contained in the aluminum plate and the content thereof are preferably Fe: 0.3-1% by mass, Si: 0.15-1% by mass, Cu: 0.1-1% by mass, Mg: 0 0.1-1.5% by mass, Mn: 0.1-1.5% by mass, Zn: 0.1-1.5% by mass, Cr: 0.01-0.1% by mass, Ti: 0.01 More preferably, the Fe content is more than 0.30 to 0.70 mass%, the Si content is 0.20 to 0.50 mass%, and the Cu content is 0.10 to 0.10 mass%. 0.50 mass%, Ti content is 0.02-0.3 mass%, Mg content is 0.50-1.5 mass%, Mn content is 0.1-1.3 mass%, The Cr content is 0.01 to 0.08% by mass, the Zn content is 0.1 to 1.3% by mass, and inevitable impurities may be included. The amount is preferably at least 95 mass%, aluminum content can also be preferably used in the range of 95 to 99.4 wt%.

  Particularly preferably, the Fe content is more than 0.40 to 0.50% by mass, the Si content is more than 0.25 to 0.30% by mass, the Cu content is 0.10 to 0.15% by mass, and Ti is contained. The amount is 0.02 to 0.05 mass%, the Mg content is 0.80 to 1.5 mass%, the Mn content is 0.10 to 1.00 mass%, and the Cr content is 0.01 to An aluminum plate having 0.05% by mass, Zn content of 0.1 to 0.3% by mass and the balance of Al content of 95 to 99.4% by mass and inevitable impurities is used.

  Different elements in the aluminum plate have a significant effect on the uniformity of the pits generated in the electrochemical surface roughening treatment, and can achieve a good balance between printing durability, stain resistance and exposure stability. In order for the pits to generate, it is necessary to make advanced adjustments such as the type of different elements and the amount added. According to the present invention, a hydrophilic layer made of a highly hydrophilic polymer having a specific side chain structure is used to form a support using an organic polymer such as a resin or an aluminum material with a high content of foreign elements. Even when the support is used, it is possible to produce an excellent lithographic printing plate precursor that gives good printing performance.

  Below, the preferable content of the different element which may be contained in the aluminum material used for the support body formation of this invention, and the influence at the time of producing a support body are demonstrated in detail.

Fe is an element contained in a new metal in the range of about 0.1 to 0.2% by mass, and the amount dissolved in aluminum is small, and most remains as an intermetallic compound. Fe has an effect of increasing the mechanical strength of the aluminum plate. However, if it is more than 1% by mass, cracking is likely to occur during rolling, and if the Fe content is less than 0.15% by mass, the mechanical strength is low. As a result, problems such as a decrease in yield may occur during rolling.
In the present invention, the Fe content is 0.3 to 1% by mass. Preferably, it is more than 0.30 to 0.70% by mass, and more preferably more than 0.30 to 0.50% by mass.

Si is an element contained in the new metal also in the range of about 0.02 to 0.1% by mass. Si exists as a solid solution in aluminum or as an intermetallic compound or a single precipitate. Further, when heated during the production process of a lithographic printing plate support, Si that has been dissolved may precipitate as a simple substance i. According to the knowledge of the present inventors, when the elemental Si is excessive, the solid solution Si is likely to precipitate as the elemental Si, and the severe ink stain resistance may be lowered.
Further, the Si content affects the electrochemical surface roughening of the aluminum plate, and if it is less than 0.03% by mass, the pits may be dissolved in the electrochemical surface roughening treatment and a uniform surface structure may not be obtained. .
In the present invention, the Si content is 0.15 to 1% by mass. Preferably it is 0.20 to 0.50 mass%, More preferably, it is more than 0.20 to 0.40 mass%.

Cu is an element contained in a lot of scraps of JIS 2000 series and 4000 series materials, and is relatively easily dissolved in Al.
The Cu content greatly affects the electrochemical surface roughening treatment. In particular, in an electrochemical surface roughening treatment using alternating current in an electrolytic solution containing nitric acid (hereinafter simply referred to as “nitric acid alternating current electrolysis”), if the Cu content is less than 0.0001% by mass, electrolysis is performed. The latitude may become narrower with respect to temperature fluctuations.
Content of Cu is 0.1-1 mass%. Preferably, it is 0.10-0.50 mass%, More preferably, it is 0.10-0.30 mass%.

Ti is an element that is usually added in an amount of 0.005 to 0.04 mass% as a crystal refining material. JIS 5000 series, 6000 series, and 7000 series scraps contain relatively large amounts of impurity metals. The Ti content affects the degree of crystal refinement (the degree of crystal grain size of the aluminum plate) and the electrochemical surface roughening. If the Ti content is less than 0.0010% by mass, the effect of crystal refining may not be observed.
The Ti content is 0.01 to 0.5% by mass. Preferably, it is 0.02-0.3 mass%, More preferably, it is 0.02-0.05 mass%.

The Mg content affects the electrochemical surface roughening treatment. If the Mg content is less than 0.0001% by mass, an unetched part is likely to occur in nitric acid AC electrolysis.
The content of Mg is 0.1 to 1.5% by mass. Preferably, it is 0.30-1.5 mass%, More preferably, it is 0.50-1.35 mass%.

The Mn content affects the electrochemical surface roughening treatment. If the Mn content is less than 0.0001% by mass, an unetched portion is likely to occur in hydrochloric acid alternating current electrolysis.
The Mn content is 0.1 to 1.5% by mass. Preferably, it is 0.30-1.40 mass%, More preferably, it is 0.50-1.30 mass%.

When Cr and Zn are added in an amount of 0.00005% by mass or more, the effect of improving the resistance to severe ink stains is exhibited. Affects the surface structure. That is, they affect the microstructure in minimal etching. Cr is a foreign element contained in a small amount in JIS A5000-series, 6000-series, and 7000-series scraps.
Moreover, when there is too much these content, since an effect will be saturated and it will become disadvantageous in cost, it is unpreferable. In the present invention, the Cr content is 0.01 to 0.1% by mass, preferably 0.01 to 0.08% by mass, and more preferably the Cr content is 0.01 to 0.05% by mass. %.
Zn content is 0.1-1.5 mass%. Preferably, it is 0.1-1.3 mass%, More preferably, it is 0.1-0.3 mass%.

  In order to use an aluminum alloy as a plate material, for example, the following method can be employed. First, a molten aluminum alloy adjusted to a predetermined alloy component content is subjected to a cleaning process and cast according to a conventional method. In the cleaning process, in order to remove unnecessary gas such as hydrogen in the molten metal, flux treatment, degassing process using argon gas, chlorine gas, etc., so-called rigid media filter such as ceramic tube filter, ceramic foam filter, A filtering process using a filter that uses alumina flakes, alumina balls or the like as a filter medium, a glass cloth filter, or a combination of a degassing process and a filtering process is performed.

  These cleaning treatments are preferably performed in order to prevent defects caused by foreign matters such as non-metallic inclusions and oxides in the molten metal and defects caused by gas dissolved in the molten metal. Regarding filtering of the molten metal, JP-A-6-57432, JP-A-3-162530, JP-A-5-140659, JP-A-4-231425, JP-A-4-276031, JP-A-5-311261, JP-A-5-311261 6-136466 and the like. Further, the degassing of the molten metal is described in JP-A-5-51659, Japanese Utility Model Laid-Open No. 5-49148, and the like. The applicant of the present application has also proposed a technique relating to degassing of molten metal in Japanese Patent Application Laid-Open No. 7-40017.

Next, casting is performed using the molten metal that has been cleaned as described above. As for the casting method, there are a method using a solid mold typified by a DC casting method and a method using a driving mold typified by a continuous casting method.
In DC casting, solidification occurs at a cooling rate in the range of 0.5 to 30 ° C./second. When the temperature is less than 1 ° C., many coarse intermetallic compounds may be formed. When DC casting is performed, an ingot having a thickness of 300 to 800 mm can be produced. The ingot is chamfered as necessary according to a conventional method, and usually 1 to 30 mm, preferably 1 to 10 mm, of the surface layer is cut. Before and after that, soaking treatment is performed as necessary. When performing the soaking process, heat treatment is performed at 450 to 620 ° C. for 1 to 48 hours so that the intermetallic compound does not become coarse. If the heat treatment is shorter than 1 hour, the effect of soaking may be insufficient. In addition, when soaking is not performed, there is an advantage that the cost can be reduced.

  Then, hot rolling and cold rolling are performed to obtain a rolled aluminum plate. An appropriate starting temperature for hot rolling is 350 to 500 ° C. An intermediate annealing treatment may be performed before or after hot rolling or in the middle thereof. The conditions for the intermediate annealing treatment are heating at 280 to 600 ° C. for 2 to 20 hours, preferably 350 to 500 ° C. for 2 to 10 hours using a batch annealing furnace, or 400 to 600 ° C. using a continuous annealing furnace. Heating is performed for 6 minutes or less, preferably 450 to 550 ° C. for 2 minutes or less. The crystal structure can be made finer by heating at a heating rate of 10 to 200 ° C./second using a continuous annealing furnace.

The flatness of the aluminum plate finished to a predetermined thickness, for example, 0.1 to 0.5 mm by the above steps may be further improved by a correction device such as a roller leveler or a tension leveler. The flatness may be improved after the aluminum plate is cut into a sheet shape, but in order to improve productivity, it is preferably performed in a continuous coil state. Further, a slitter line may be used for processing into a predetermined plate width. Moreover, in order to prevent generation | occurrence | production of the damage | wound by friction between aluminum plates, you may provide a thin oil film on the surface of an aluminum plate.
As the oil film, a volatile or non-volatile film is appropriately used as necessary.

  The aluminum plate used in the present invention is preferably subjected to H18 tempering as defined in JIS.

Various characteristics described below are desired for the aluminum plate thus manufactured.
As for the strength of the aluminum plate, it is preferable that the 0.2% proof stress is 120 MPa or more in order to obtain the stiffness required for a lithographic printing plate support. Moreover, in order to obtain a certain level of waist strength even when performing a burning treatment, the 0.2% yield strength after heat treatment at 270 ° C. for 3 to 10 minutes is preferably 80 MPa or more, and 100 MPa or more. It is more preferable that The 0.2% proof stress is described in RIKEN Encyclopedia 4th edition (Iwanami Shoten), page 743, and can be measured by using a general-purpose tensile tester.
In particular, when you want the stiffness of the aluminum plate, you can use the aluminum material added with Mg and Mn, but if you strengthen the stiffness, it will be easier to fit the plate cylinder of the printing press, Depending on the material, the material and the amount of the trace component added are appropriately selected.
Further, the aluminum plate preferably has a tensile strength of 140 to 300 N / mm ² and an elongation specified by JIS Z2241 and Z2201 of 1 to 10%.

The crystal structure of the aluminum plate may cause poor surface quality when the surface of the aluminum plate is subjected to chemical or electrochemical surface roughening. It is preferably not too coarse. The crystal structure on the surface of the aluminum plate preferably has a width of 200 μm or less, more preferably 100 μm or less, still more preferably 50 μm or less, and the length of the crystal structure is 5000 μm or less. Is preferably 1000 μm or less, and more preferably 500 μm or less.
The thickness of the aluminum plate used as a support in the present invention is about 0.1 mm to 0.6 mm, preferably 0.15 mm to 0.4 mm, and particularly preferably 0.2 mm to 0.3 mm.

In producing the aluminum support, the aluminum plate may be subjected to surface treatment such as roughening treatment, anodizing treatment, silicate treatment, etc., if necessary. Hereinafter, such a surface treatment will be briefly described.
Prior to roughening the aluminum plate, a degreasing treatment with, for example, a surfactant, an organic solvent, or an alkaline aqueous solution for removing rolling oil on the surface is performed as desired.
The surface roughening treatment of the aluminum plate is performed by various methods. For example, a method of mechanically roughening, a method of electrochemically dissolving and roughening a surface, and a method of selectively dissolving a surface chemically. This is done by the method of As the mechanical method, a known method such as a ball polishing method, a brush polishing method, a blast polishing method, or a buff polishing method can be used. Further, as an electrochemical surface roughening method, there is a method of performing alternating current or direct current in hydrochloric acid or nitric acid electrolyte. Further, as disclosed in JP-A-54-63902, a method in which both are combined can also be used.

  For aluminum plates with low aluminum purity, from the viewpoint of achieving good and uniform roughening, a method of mechanically roughening, a method of electrochemically dissolving and roughening the surface, and a surface of chemical In some cases, it may be difficult to perform part or all of the method for selectively dissolving the surface hydrophilicity, but even in that case, by forming an intermediate layer composed of a specific polymer described later in the present invention, surface hydrophilicity, Further, it is possible to obtain a lithographic printing plate support having good adhesion to the image forming layer.

  The roughened aluminum plate is subjected to alkali etching treatment and neutralization treatment as necessary, and then subjected to anodization treatment if desired in order to enhance the water retention and wear resistance of the surface. As the electrolyte used for the anodizing treatment of the aluminum plate, various electrolytes that form a porous oxide film can be used. In general, sulfuric acid, phosphoric acid, oxalic acid, chromic acid, or a mixed acid thereof is used. The concentration of these electrolytes is appropriately determined depending on the type of electrolyte.

The treatment conditions for anodization vary depending on the electrolyte used, and thus cannot be specified in general. In general, however, the electrolyte concentration is 1 to 80% by mass solution, the liquid temperature is 5 to 70 ° C., and the current density is 5 to 60 A / dm ^2. A voltage of 1 to 100 V and an electrolysis time of 10 seconds to 5 minutes are suitable. If the amount of the formed anodized film is less than 1.0 g / m ² , the printing durability is insufficient, or the non-image part of the lithographic printing plate is likely to be damaged, and ink is applied to the damaged part during printing. So-called “scratch dirt” is likely to occur.

(Silicate processing)
When the support is made of an aluminum material, the aluminum substrate is preferably subjected to a silicate treatment on the surface of the aluminum substrate obtained as described above from the viewpoint of improving the adhesion strength with the hydrophilic layer.
The method for applying the silicate treatment is not particularly limited, and any conventionally known method can be arbitrarily used. For example, there is a method of immersing the aluminum base in an aqueous solution in which an alkali metal silicate is dissolved. Can be mentioned.
In this case, the concentration of the aqueous alkali silicate solution is preferably about 1 to 30% by mass, and more preferably about 2 to 15% by mass. The pH of the aqueous solution is preferably about 10 to 13 at 25 ° C. In the silicate treatment according to the present invention, such an aqueous solution is kept at 15 to 80 ° C., preferably 15 to 50 ° C., and the aluminum substrate is immersed in the aqueous solution for 0.5 to 120 seconds, preferably 5 to 60 seconds. Is implemented.

As the alkali metal silicate used for the silicate treatment, sodium silicate, potassium silicate, lithium silicate, or the like is used.
In addition, a hydroxide may be added to the alkali metal silicate aqueous solution in order to increase the pH of the aqueous solution. Examples of such hydroxide include sodium hydroxide, potassium hydroxide, lithium hydroxide and the like. The amount of the hydroxide added is preferably about 0.01 to 10% by mass in the aqueous solution, and more preferably about 0.05 to 5.0% by mass.
In addition, alkaline earth metal salts or Group IVB metal salts may be added. Such alkaline earth metal salts include nitrates such as calcium nitrate, strontium nitrate, magnesium nitrate and barium nitrate, sulfates, hydrochlorides, phosphates, acetates, oxalates, borates, etc. A water-soluble salt is mentioned. Group IVB metal salts include titanium tetrachloride, titanium trichloride, potassium fluoride titanium, potassium oxalate, titanium sulfate, titanium tetraiodide, zirconium chloride, zirconium dioxide, zirconium oxychloride, zirconium tetrachloride, etc. Can be mentioned. Such alkaline earth metal salts or Group IVB metal salts can be used alone or in combination of two or more. The addition amount of the metal salt is preferably about 0.01 to 10% by mass in the aqueous solution, and more preferably about 0.05 to 5.0% by mass.

  As another method of silicate treatment, silicate electrodeposition as described in US Pat. No. 3,658,662 is also effective. Combining a support with electrolytic grains as disclosed in JP-B-46-27481, JP-A-52-58602, JP-A-52-30503, and the above-mentioned anodizing treatment and hydrophilization treatment with silicate. Surface treatment etc. can also be applied.

The metal silicate film obtained by such a silicate treatment is formed with a Si element amount of ^{2 to} 40 mg / m ² , more preferably 4 to 30 mg / m ² . The amount of film can be measured by fluorescent X-ray analysis.

<Hydrophilic layer>
In the lithographic printing plate precursor according to the invention, on the support, a reactive group capable of directly chemically bonding to the support surface and a reactivity capable of chemically bonding to the support surface via a component having a crosslinked structure. It comprises a hydrophilic layer (hereinafter referred to as a specific hydrophilic layer as appropriate) formed by chemical bonding of at least one reactive group of groups and a hydrophilic polymer having a specific functional group. And
Hereinafter, the polymer constituting such a specific hydrophilic layer will be described.
[(1) The structural unit (i) in the general formula (1) having at least one reactive group among the reactive groups capable of being chemically bonded to the support surface through a component having a crosslinked structure. And a polymer containing the structural unit (ii) [specific polymer (1)]
The specific polymer (1) according to the present invention is characterized by containing at least the structural unit (i) and the structural unit (ii) in the following general formula (1). That is, the specific polymer (1) has a silane coupling group represented by the structural unit (i) at the end of a structure in which a plurality of repeating units represented by the structural unit (ii) are linked, And a reactive group capable of binding to the support directly or via a crosslinking component.

Here, as the reactive group capable of directly chemically bonding to the aluminum substrate surface, a functional group capable of being chemically bonded to a functional group such as -Al ³⁺ or -OH present on the aluminum substrate surface, such as a hydroxysilyl group, Examples include alkoxysilyl groups, aryloxysilyl groups, halosilyl groups (such as chlorosilyl groups), and aminosilyl groups. When a support made of an organic material is used, for example, hydroxysilyl groups, alkoxysilyl groups Aryloxysilyl group, halosilyl group (chlorosilyl group and the like), aminosilyl group, and the like.

Examples of the reactive group that can be chemically bonded to the surface of the aluminum substrate through a component having a crosslinked structure include, for example, a hydroxysilyl group, an alkoxysilyl group, an aryloxysilyl group, a halosilyl group (chlorosilyl group, etc.) Functional groups such as a group, a hydroxyl group, an amino group, an epoxy group, a carboxyl group, and a vinyl group, and the same functional group as that for an aluminum substrate is preferably used for an organic material substrate such as a plastic film. . In the latter case, the component having a crosslinked structure with the surface of the aluminum substrate refers to a component such as a sol-gel crosslinking component, a compound containing a vinyl polymerizable group, an epoxy polymerizable group, an oxetane polymerizable group, etc., which will be described later.
Such a reactive group may be located at either the end or the side chain of the chain structure of the hydrophilic polymer, but is preferably located at the end from the viewpoint of high water retention, and from the viewpoint of membrane strength, the side chain is preferred. It is preferable to select or combine them appropriately.

  In the polymer main chain structure composed of repeating units represented by the structural unit (ii) in the general formula (1), the structural unit (ii) may be one type or two or more types, and the structural unit (ii) ) Other than the copolymer component may be included.

In the general formula (1), R ¹ , R ² , R ³ , and R ⁴ each independently represent a hydrogen atom or a substituent having 1 to 30 carbon atoms.
Preferably, it is a substituent containing 1 to 20 carbon atoms in the structure, more preferably a substituent having 1 to 15 carbon atoms, and particularly preferably a substituent having 1 to 8 carbon atoms.
Examples of the substituent when R ¹ , R ² , R ³ , and R ⁴ represent a substituent having 1 to 30 carbon atoms include a linear, branched, or cyclic alkyl group, an aryl group, and a heterocyclic group.
Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, isopropyl, isobutyl, s-butyl, t-butyl, isopentyl, A neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group and the like can be mentioned. Examples of the aryl group include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. Examples of the heterocyclic group include a furanyl group, a thiophenyl group, and a pyridinyl group.

These groups may further have a substituent. As the substituent, a monovalent nonmetallic atomic group excluding hydrogen is used. Preferred examples include halogen atoms (-F, -Br, -Cl, -I), hydroxyl groups, alkoxy groups, aryloxy groups, mercapto groups, alkylthio groups, arylthio groups, alkyldithio groups, aryldithio groups, amino groups, N-alkylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, ア ル キ ル -alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkyl Carbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group, acylthio group, acylamino group, N-alkylacylamino group, N-aryl Acylamino group, ureido group, N ′ Alkylureido group, N ′, N′-dialkylureido group, N′-arylureido group, N ′, N′-diarylureido group, N′-alkyl-N′-arylureido group, N-alkylureido group, N -Arylureido group, N'-alkyl-N-alkylureido group, N'-alkyl-N-arylureido group, N ', N'-dialkyl-N-alkylureate group, N', N'-dialkyl- N-arylureido group, N′-aryl-Ν-alkylureido group, N′-aryl-N-arylureido group, N ′, N′-diaryl-N-alkylureido group, N ′, N′-diaryl- N-arylureido group, N′-alkyl-N′-aryl-N-alkylureido group, N′-alkyl-N′-aryl-N-arylureido group, alkoxycarbonylamino group Aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino Group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group , N-alkyl-N-arylcarbamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (—SO ₃ H) and its conjugate base group (hereinafter referred to as sulfonate group), al Coxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N -Alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N- alkyl -N- arylsulfamoyl group phosphono group _(-PO 3 _{H 2)} and its conjugated base group (hereinafter referred to as phosphonato group), a dialkyl phosphono group _(-PO 3 _(alkyl) 2), Jiariruhosu phono group _{(-PO 3 (aryl) 2)} , alkyl aryl phosphono group (-P ₃ (alkyl) (aryl)), monoalkyl phosphono group _(-PO 3 H (alkyl)) and its conjugated base group (hereinafter referred to as alkyl phosphonophenyl group), monoaryl phosphono group _(-PO 3 H ( aryl)) and its conjugate base group (hereinafter referred to as arylphosphonate group), phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as phosphonateoxy group), dialkylphosphonooxy Group (—OPO ₃ (alkyl) ₂ ), diarylphosphonooxy group (—OPO ₃ (aryl) ₂ ), alkylarylphosphonooxy group (—OPO (alkyl) (aryl)), monoalkylphosphonooxy group ( -OPO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkylphosphonatooxy group) ), Monoarylphosphonooxy group (—OPO ₃ H (aryl)) and its conjugate base group (hereinafter referred to as arylphosphonatooxy group), morpholino group, cyano group, nitro group, aryl group, alkenyl group, An alkynyl group is mentioned.

Examples of R ¹ , R ² , R ³ and R ⁴ include a hydrogen atom, a methyl group, and an ethyl group as particularly preferable examples from the viewpoints of effects and availability.

L ¹ in the general formula (1) and L ² in the general formula (2) described later represent a single bond or an organic linking group. Here, the organic linking group refers to a polyvalent linking group composed of a nonmetallic atom, and specifically includes 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, and 0 to 50 carbon atoms. It consists of up to 1 oxygen atom, 1 to 100 hydrogen atoms, and 0 to 20 sulfur atoms. More specific examples of the organic linking group include the following structural units or combinations thereof.

A particularly preferred structure for L ¹ includes — (CH ₂ ) _n —S—. Here, n is preferably an integer of 1 to 8, more preferably 1 to 5, and particularly preferably 2 to 4.
As L ² , particularly preferable structures include a single bond and those shown below.

Y ¹ represents a C 1-30 substituent having at least a structure selected from —CO—NH—CO—, —CO—NH—SO ₂ —, and —SO ₂ —NH—SO ₂ —. The structure represented by Y ¹ may be chain-like, branched or cyclic. Y ¹ and R ³ may be bonded to form a cyclic structure.

Preferable examples of Y ¹ include the following.
In the following examples, * indicates a bonding site with a carbon atom constituting the polymer main chain.
* —C (═O) —NH—SO ₂ —CH <sub>3
* -C (= O) -NH-</sub> SO 2 -C 2 H 5
* —C (═O) —NH—SO ₂ —C ₃ H ₇
* —C (═O) —NH—SO ₂ —CH (CH ₃ ) ₂
* —C (═O) —NH—SO ₂ —C ₄ H ₉
* —C (═O) —NH—SO ₂ —C ₅ H ₁₁
* —C (═O) —NH—SO ₂ —C ₆ H ₁₂
* —C (═O) —NH—SO ₂ —C ₆ H ₅
* —C (═O) —NH—C (═O) —CH ₃
* -C (= O) -NH- C (= O) -C 2 H 5
* -C (= O) -NH- C (= O) -C 3 H 7
* -C (= O) -NH- C (= O) -CH (CH 3) 2
* -C (= O) -NH- C (= O) -C 4 H 9
* -C (= O) -NH- C (= O) -C 5 H 11
* -C (= O) -NH- C (= O) -C 6 H 12
* -C (= O) -NH- C (= O) -C 6 H 5
_{* -SO 2 -NH-SO 2 -CH} 3
_{* -SO 2 -NH-SO 2 -C} 2 H 5
_{* -SO 2 -NH-SO 2 -C} 3 H 7
_{* -SO 2 -NH-SO 2 -CH} (CH 3) 2
_{* -SO 2 -NH-SO 2 -C} 4 H 9
_{* -SO 2 -NH-SO 2 -C} 5 H 11
_{* -SO 2 -NH-SO 2 -C} 6 H 12
_{* -SO 2 -NH-SO 2 -C} 6 H 5
* —SO ₂ —NH—C (═O) —CH <sub>3
* -SO 2 -NH-C (=</sub> O) -C 2 H 5
* —SO ₂ —NH—C (═O) —C ₃ H ₇
* —SO ₂ —NH—C (═O) —CH (CH ₃ ) ₂
* —SO ₂ —NH—C (═O) —C ₄ H ₉
* —SO ₂ —NH—C (═O) —C ₅ H ₁₁
* —SO ₂ —NH—C (═O) —C ₆ H ₁₂
* —SO ₂ —NH—C (═O) —C ₆ H ₅

Y ¹ may further have a substituent, and examples of preferable substituents that can be introduced include linear, branched or cyclic alkyl groups, aryl groups, alkenyl groups, alkynyl groups, heterocyclic groups, and halogen atoms. (-F, -Br, -Cl, -I), hydroxyl group, alkoxy group, aryloxy group, alkylthio group, amino group (including substituted amino group), formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryl Examples include a loxycarbonyl group and a sulfo group (—SO ₃ H). When a plurality of substituents are introduced, these may be the same or different from each other, and the plurality of substituents may be bonded to each other to form a ring.

  In the present invention, the compound represented by the general formula (1) may be a copolymer having a single structural unit or a plurality of components represented by (ii). Furthermore, a copolymer component other than the structural unit represented by (ii) may be included.

  The molecular weight of the specific polymer (1) is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, and most preferably 1,000 to 30,000.

Although the specific example of the polymer (1) used suitably for this invention is shown by the weight average molecular weight (Mw) measured by the structural unit and GPC method, this invention is not limited to these.

[Having at least one reactive group of a reactive group that can be chemically bonded directly to the support surface and a reactive group that can be chemically bonded to the support surface via a component having a cross-linked structure; Polymer containing the structural unit (iii) and the structural unit (iv) in the general formula (2) [specific polymer (2)]
In another preferred embodiment of the polymer constituting the hydrophilic layer in the present invention, the polymer is chemically bonded via a reactive group capable of directly chemically bonding to the support surface and a component having a crosslinked structure with the support surface. The polymer which has at least 1 sort (s) of reactive group of possible reactive groups, and contains structural unit (iii) and structural unit (iv) in following General formula (2) is mentioned.

The specific polymer (2) will be described.
The specific polymer (2) is a polymer compound having both a repeating unit of a structural unit (iii) having a silane coupling group and a structural unit (iv) having a specific functional group represented by Y ² It is. In addition, the structural unit (iii) and the structural unit (iv) may be single or a plurality of types may be combined, respectively. Further, a repeating unit other than the structural unit (iii) and the structural unit (iv) Component).
In the general formula (2), the molar composition ratio of the structural unit (iii) to the structural unit (iv) is preferably 99.5: 0.5 to 0.5: 99.5, and 99: 1 to 50:50 is more preferable, and 98: 2 to 70:30 is particularly preferable.

R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ each independently represent a hydrogen atom or a substituent having 1 to 30 carbon atoms. Preferably, it is a substituent containing 1 to 20 carbon atoms in the structure, more preferably a substituent having 1 to 15 carbon atoms, and particularly preferably a substituent having 1 to 8 carbon atoms.
Examples of R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ include linear, branched or cyclic alkyl groups, aryl groups, and heterocyclic groups.
Specific examples of R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ include examples of R ¹ , R ² , R ^3, and R ^{4 in} the description of the general formula (1). As mentioned above, the same may be mentioned.

L ² represents a single bond or an organic linking group. Specific examples of L ² are the same as those of L ¹ described above.

Y ² represents a substituent having 1 to 30 carbon atoms having at least a structure selected from —CO—NH—CO—, —CO—NH—SO ₂ —, and —SO ₂ —NH—SO ₂ —. A substituent having 1 to 30 carbon atoms is represented. Specific examples of Y ² include the same examples as Y ¹ in the general formula (1), and preferred examples are also the same.

The molecular weight of the compound of the general formula (2) is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, and particularly preferably 1,000 to 30,000.
Specific examples of the specific polymer (2) that can be suitably used in the present invention are shown below by the structural unit and the weight average molecular weight (Mw) measured by the GPC method, but the present invention is not limited to these. .

  The specific polymer (1) or the specific polymer (2) can be synthesized by any known method, and a radical polymerization method is preferably used for the synthesis. General radical polymerization methods include, for example, New Polymer Experiments 3, Polymer Synthesis and Reaction 1 (Polymer Society, Kyoritsu Publishing), New Experimental Chemistry Course 19, Polymer Chemistry (I) (The Chemical Society of Japan) , Maruzen), Materials Engineering Course, Synthetic Polymer Chemistry (Tokyo Denki University Press), etc., and these can be applied.

Further, as described above, the specific polymer (1) and the specific polymer (2) are the structural unit (i), the structural unit (ii) in the general formula (1), or the general formula (2). The copolymer may have a structural unit other than the structural unit (iii) and the structural unit (iv).
Here, the structural unit that can be used in combination is derived from various known monomers in addition to those represented by the structural unit (i), the structural unit (ii), the structural unit (iii), and the structural unit (iv). The structure to do can be mentioned.
Preferred examples include known monomers derived from acrylic esters, methacrylic esters, acrylamides, methacrylamides, vinyl esters, styrenes, acrylic acid, methacrylic acid, acrylonitrile, maleic anhydride, maleic imide, etc. Things. By carrying out such copolymerization, various physical properties such as film forming property, film strength, hydrophilicity, hydrophobicity, solubility, reactivity and stability can be improved or controlled.

  Specific examples of acrylic esters include methyl acrylate, ethyl acrylate, (n- or i-) propyl acrylate, (n-, i-, sec- or t-) butyl acrylate, amyl acrylate, 2-ethylhexyl acrylate, Dodecyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypentyl acrylate, cyclohexyl acrylate, allyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, benzyl acrylate, methoxybenzyl acrylate, chloro Benzyl acrylate, hydroxybenzyl acrylate, hydroxyphenethyl acrylate, dihydroxyphenethyl Acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, hydroxyphenyl acrylate, chlorophenyl acrylate, sulfamoylphenyl acrylate, 2- (hydroxyphenyl carbonyloxy) ethyl acrylate.

  Specific examples of methacrylic acid esters include methyl methacrylate, ethyl methacrylate, (n- or i-) propyl methacrylate, (n-, i-, sec- or t-) butyl methacrylate, amyl methacrylate, 2-ethylhexyl methacrylate, Dodecyl methacrylate, chloroethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxypentyl methacrylate, cyclohexyl methacrylate, allyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, benzyl methacrylate, methoxybenzyl methacrylate, chloro Benzyl methacrylate, hydroxybenzyl methacrylate, hydroxyphene Chill methacrylate, dihydroxyphenethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, hydroxyphenyl methacrylate, chlorophenyl methacrylate, sulfamoylphenyl methacrylate, 2- (hydroxyphenyl carbonyloxy) ethyl methacrylate.

  Specific examples of acrylamides include acrylamide, N-methylacrylamide, N-ethylacrylamide, N-propylacrylamide, N-butylacrylamide, N-benzylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, and N-tolylacrylamide. N- (hydroxyphenyl) acrylamide, N- (sulfamoylphenyl) acrylamide, N- (phenylsulfonyl) acrylamide, N- (tolylsulfonyl) acrylamide, N, N-dimethylacrylamide, N-methyl-N-phenylacrylamide , N-hydroxyethyl-N-methylacrylamide and the like.

  Specific examples of methacrylamides include methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-propylmethacrylamide, N-butylmethacrylamide, N-benzylmethacrylamide, N-hydroxyethylmethacrylamide, N -Phenylmethacrylamide, N-tolylmethacrylamide, N- (hydroxyphenyl) methacrylamide, N- (sulfamoylphenyl) methacrylamide, N- (phenylsulfonyl) methacrylamide, N- (tolylsulfonyl) methacrylamide, N , N-dimethylmethacrylamide, N-methyl-N-phenylmethacrylamide, N-hydroxyethyl-N-methylmethacrylamide and the like.

Specific examples of vinyl esters include vinyl acetate, vinyl butyrate, vinyl benzoate, and the like. Specific examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, propyl styrene, cyclohexyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene, acetoxymethyl styrene, methoxy styrene, dimethoxy styrene. Chlorostyrene, dichlorostyrene, bromostyrene, iodostyrene, fluorostyrene, carboxystyrene, and the like.
As the copolymerization component, a structural unit represented by the following formula (v) [hereinafter referred to as a structural unit (v)] is particularly preferable.

R ³ and R ⁴ in the structural unit (v) each independently represent a hydrogen atom or a substituent having 1 to 30 carbon atoms, L ⁵ represents a single bond or an organic linking group, and Y ³ represents 1 to 30 carbon atoms. Represents a substituent.
The R ^3, R ^4, the same as R ^3, R ⁴ in the structural unit (iii) are exemplified, and among them, particularly preferred examples from the viewpoints of effects and easiness of availability, a hydrogen atom, a methyl group or An ethyl group can be mentioned. Further, L ⁵ is exemplified by the same as L ¹ in the general formula (1), and preferred examples are also the same.

Examples of Y ^3, from the viewpoint of maintaining the surface hydrophilicity of a particular intermediate _{^{layer, -CONH 2, -CON (R 11}} ) (R 12), - CO 2 R 13, -OH, -CO 2 M, or -SO ₃ M are preferably mentioned. When Y ³ represents any of these substituents, L ⁵ is preferably a single bond.
Here, R <^11> , R < ¹² >, and R < ¹³ > represent a hydrogen atom or a C1-C30 substituent each independently. Preferably, it is C1-C20, More preferably, it is C1-C15, Most preferably, it is C1-C8. Examples of R ¹¹ , R ¹² , and R ¹³ include linear, branched, or cyclic alkyl groups, aryl groups, and heterocyclic groups. R ¹¹ and R ¹² may be bonded to each other to form a ring. Preferable examples include the preferred examples of R ¹ , R ² , R ³ and R ⁴ described above.
A most preferred example of the structural unit (v) includes a structure in which L ⁵ is a single bond and Y ³ is represented by —CONH ₂ .

(Crosslinking component)
As the surface according to the present invention, a crosslinkable group in the polymer is chemically bonded to a functional group such as —SiO ^— Na ⁺ , —Al ³⁺ , or —OH group directly on the surface of a support (for example, aluminum). Alternatively, a crosslinked solution (sol-gel crosslinked structure) is formed by preparing a coating solution containing the above-mentioned polymer, applying it to the surface of the base material, and drying, thereby hydrolyzing and condensing the crosslinking group. It may be.
In forming the sol-gel cross-linked structure, it is preferable to mix a specific hydrophilic polymer and a cross-linking component represented by the following general formula (3), and apply and dry to the substrate surface. The crosslinking component represented by the following general formula (3) is a compound having a polymerizable functional group in its structure and functioning as a crosslinking agent, and by condensation polymerization with the specific hydrophilic polymer. A strong film having a crosslinked structure is formed.

In the general formula (3), R ¹⁴ represents a hydrogen atom, an alkyl group or an aryl group, R ¹⁵ represents an alkyl group or an aryl group, X represents Si, Al, Ti or Zr, and n is 0 to 2. Represents an integer.
The number of carbon atoms when R ¹⁴ and R ¹⁵ represent an alkyl group is preferably 1 to 4. The alkyl group or aryl group may have a substituent, and examples of the substituent that can be introduced include a halogen atom, an amino group, and a mercapto group.
This compound preferably has a molecular weight of 1000 or less.

Specific examples of the crosslinking component represented by the general formula (3) are given below, but the present invention is not limited thereto.
In the case where X is Si, that is, those containing silicon in the hydrolyzable compound include, for example, trimethoxysilane, triethoxysilane, tripropoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, methyltrimethoxy Silane, ethyltriethoxysilane, propyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, dimethyldimethoxysilane, diethyldiethoxysilane, γ-chloropropyltriethoxysilane, γ-mercaptopropyltri Methoxysilane, γ-mercaptopropyltriethoxysilane, γ-aminopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, diph Alkenyl dimethoxysilane, mention may be made of diphenyl diethoxy silane.
Among these, tetramethoxysilane, tetraethoxysilane, methyltolumethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, dimethyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxy are particularly preferable. Examples include silane, diphenyldimethoxysilane, diphenyldiethoxysilane, and the like.

  In addition, when X is Al, that is, examples of the hydrolyzable compound containing aluminum include, for example, trimethoxy aluminate, triethoxy aluminate, tripropoxy aluminate, tetraethoxy aluminate and the like. it can.

  When X is Ti, i.e., those containing titanium, for example, trimethoxy titanate, tetramethoxy titanate, triethoxy titanate, tetraethoxy titanate, tetrapropoxy titanate, chlorotrimethoxy titanate, chlorotriethoxy titanate, ethyl triethoxy titanate. Examples thereof include methoxy titanate, methyl triethoxy titanate, ethyl triethoxy titanate, diethyl diethoxy titanate, phenyl trimethoxy titanate, and phenyl triethoxy titanate.

  When X is Zr, that is, the one containing zirconium can include, for example, a zirconate corresponding to the compound exemplified as containing titanium.

[Method of forming hydrophilic layer]
<Preparation of coating solution>
In preparing the coating solution composition for forming a hydrophilic layer in the present invention, as described above, a hydrophilic polymer having a specific functional group, specifically, a specific polymer (1) or a specific polymer (2) is used. However, the content of the specific hydrophilic polymer is preferably 10% by mass or more and less than 50% by mass in terms of solid content. When the content of the specific polymer is in the above range, a coating film having a sufficient film strength, good film characteristics and no fear of cracking can be formed, which is preferable.

  In addition, when the crosslinking component as represented by the general formula (3) is added to the preparation of the coating liquid composition which is a preferred embodiment, the amount added is a specific content included in the coating liquid composition for forming a hydrophilic layer. It is preferable that the crosslinking component is added so as to be 5 mol% or more with respect to the silane coupling group in the polymer, and it is more preferable that the amount is 10 mol% or more. The upper limit of the amount of crosslinking component added is not particularly limited as long as it is within the range that can sufficiently crosslink with the polymer of the present invention, but when added excessively, the produced surface may become sticky due to the crosslinking component not involved in crosslinking. From this point of view, it is preferably at most mol%.

  The specific polymer (1) having a silane coupling group at the end of the main chain or the specific polymer (2) having a side chain, preferably further dissolving the cross-linking component in a solvent and stirring well so that these components are hydrolyzed. The organic-inorganic composite sol liquid produced by decomposing and polycondensation becomes the coating liquid composition according to the present invention, whereby the surface layer having high film strength is controlled by controlling physical properties such as hydrophilicity / hydrophobicity of the surface. It is formed. In the preparation of the organic-inorganic composite sol solution, it is preferable to use an acidic catalyst, a basic catalyst, or a metal chelate compound in combination as a catalyst in order to promote hydrolysis and polycondensation reaction. Such catalysts are essential when trying to obtain. In the present invention, it is particularly preferable to use a metal chelate compound as a catalyst.

  As the acidic catalyst or the basic catalyst, an acid or a basic compound is used as it is, or a catalyst in which it is dissolved in a solvent such as water or alcohol is used. The concentration at the time of dissolving in the solvent is not particularly limited, and may be appropriately selected according to the characteristics of the acid or basic compound used, the desired content of the catalyst, etc. Condensation rate tends to increase. However, when a basic catalyst with a high concentration is used, a precipitate may be generated in the sol solution. Therefore, when a basic catalyst is used, the concentration is preferably 1 N or less in terms of concentration in an aqueous solution.

The type of the acidic catalyst or the basic catalyst is not particularly limited. However, when it is necessary to use a catalyst having a high concentration, a catalyst composed of an element that hardly remains in the coating film after drying is preferable.
Specifically, the acid catalyst is represented by hydrogen halide such as hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, hydrogen sulfide, perchloric acid, hydrogen peroxide, carbonic acid, carboxylic acid such as formic acid or acetic acid, and its RCOOH. Examples thereof include substituted carboxylic acids in which R in the structural formula is substituted with other elements or substituents, sulfonic acids such as benzene sulfonic acid, etc., and basic catalysts include ammonia bases such as aqueous ammonia and amines such as ethylamine and aniline Etc.

  Specific examples of the metal chelate compound used in the present invention include, for example, tri-n-butoxyethyl acetoacetate zirconium, di-n-butoxybis (ethyl acetoacetate) zirconium, and n-butoxy tris (ethyl acetoacetate) zirconium. Zirconium chelate compounds such as tetrakis (n-propylacetoacetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium; diisopropoxy bis (ethyl acetoacetate) titanium Titanium chelate compounds such as acetyl acetate) titanium and diisopropoxy bis (acetylacetone) titanium; Tris (acetylacetone) aluminum , Diisopropoxyethyl acetoacetate aluminum, diisopropoxyacetylacetonate aluminum, isopropoxybis (ethylacetoacetate) aluminum, isopropoxybis (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum And aluminum chelate compounds such as aluminum and monoacetylacetonate-bis (ethylacetoacetate) aluminum. Among these metal chelate compounds, preferred are tri-n-butoxyethyl acetoacetate zirconium, diisobroxoxybis (acetylacetonato) titanium, tris (acetylacetone) aluminum, diisopropoxyethylacetoacetate aluminum, tris (ethylacetate). Acetate) aluminum. These metal chelate compounds may be used individually by 1 type, and 2 or more types may be mixed and used for them.

  The addition amount of the metal chelate compound according to the present invention is usually about 0.01 to 15% by mass, preferably 0.1 to 15% by mass, and preferably 0.1 to 10% by mass with respect to the total solid content of the coating solution. % Is more preferable.

  The coating solution is prepared by dissolving the polymer of the present invention having a silane coupling group at the end, preferably a crosslinking component, in a solvent such as water, methanol, or ethanol, and then adding the catalyst as desired and stirring. Can be implemented. The reaction temperature is from room temperature to 80 ° C., and the reaction time, that is, the time for which stirring is continued is preferably in the range of 1 to 72 hours. By this stirring, hydrolysis and polycondensation of both components are advanced, and organic inorganic A composite sol solution can be obtained.

  The solvent used in preparing the coating liquid composition containing the specific polymer and preferably a crosslinking component is not particularly limited as long as it can uniformly dissolve and disperse these, but for example, methanol, ethanol An aqueous solvent such as water is preferred.

  As described above, the preparation of the organic-inorganic composite sol liquid (coating liquid composition) for forming the hydrophilic layer according to the present invention utilizes the sol-gel method. Regarding the sol-gel method, Sakuo Sakuo “Science of Sol-Gel Method”, Agne Jofusha (published) (1988), Satoshi Hirashima “Functional Thin Film Formation Technology by the Latest Sol-Gel Method” General Technology Center (Published) (1992) and the like, and the methods described therein can be applied to the preparation of the coating liquid composition according to the present invention.

  In addition to the above, in the coating liquid composition for forming a hydrophilic layer, control of the degree of hydrophilicity / hydrophobicity, improvement of physical strength, improvement of dispersibility between the components constituting the layer, improvement of coating property, printability Various objective compounds such as improvement of the above can be added. For example, a plasticizer, a pigment, a coloring matter, a surfactant, fine particles, and the like can be given.

  The fine particles are not particularly limited but preferably include silica, alumina, titanium oxide, magnesium oxide, magnesium carbonate, calcium alginate and the like. These can be used for promoting hydrophilicity or strengthening the film. More preferably, it is silica, alumina, titanium oxide or a mixture thereof.

  Silica has many hydroxyl groups on the surface, and the inside constitutes a siloxane bond (—Si—O—Si—). In the present invention, silica that can be preferably used is ultrafine silica particles having a particle diameter of 1 to 100 nm dispersed in water or a polar solvent, also referred to as colloidal silica. Specifically, it is described in Toshiro Kaga and Hayashi Hayashi, “Applied Technology of High-Purity Silica”, Volume 3, CMC Co., Ltd. (1991).

  Alumina that can be preferably used is an alumina hydrate (boehmite) having a colloidal size of 5 to 200 nm, an anion in water (for example, a halogen atom ion such as a fluorine ion or a chlorine ion, an acetate ion). Or the like, as a stabilizer. Titanium oxide that can be preferably used is an anatase type or rutile type titanium oxide having an average primary particle size of 50 to 500 nm dispersed in water or a polar solvent using a dispersant as required. is there.

  In the present invention, the average primary particle size of hydrophilic particles that can be preferably used is 1 to 5000 nm, and more preferably 10 to 1000 nm. In the hydrophilic layer of the present invention, these hydrophilic particles may be used alone or in combination of two or more. The amount used is 5 wt% to 80 wt%, preferably 10 wt% to 70 wt%, more preferably 20 wt% to 60 wt%, based on the total solid weight of the hydrophilic layer.

The hydrophilic layer can be formed by applying and drying the hydrophilic layer-forming coating solution composition prepared as described above on the surface of the support. The thickness of the hydrophilic layer can be selected depending on the purpose, but is generally in the range of 0.01 to 3.0 g / m ² , preferably 0.01 to 1.0 g / m ^{2 in} terms of the coating amount after drying. ² , more preferably 0.03 to 1.0 g / m ² . When the coating amount is in the above range, sufficient film strength can be obtained, and the effects of the present invention such as surface hydrophilicity, adhesion to the substrate, and high sensitivity are exhibited.

[Image forming layer]
In the present invention, a lithographic printing plate precursor can be obtained by providing an image forming layer on a hydrophilic layer formed on the surface of such a support. In the present invention, the image forming layer provided here may be any known one, but from the viewpoint of effect, it is preferably an image forming layer capable of image formation by heat mode exposure such as an infrared laser. .
The image forming layer may have a single layer structure or a laminated structure composed of a plurality of layers.
Hereinafter, various planographic printing plate precursors will be described.

(Infrared laser recording type lithographic printing plate precursor)
A planographic printing plate precursor capable of forming an image by infrared exposure using an infrared laser, in which the present invention is preferably used, will be described. These contain negative or positive image-forming layers that use materials that change their solubility in alkaline aqueous solution by infrared laser exposure, and hydrophobizing precursors that can form ink-receptive regions. A known image recording method such as an image forming layer in which the region is formed is arbitrarily selected.

  First, a positive or negative image forming layer will be described. Such an image forming layer is developed with an alkaline aqueous solution after imagewise exposure with an infrared laser, the alkali developability is reduced by irradiation with actinic rays, and the negative (exposed) portion becomes an image portion region. On the contrary, the developability is improved, and the irradiation (exposure) portion is divided into two types, that is, a non-image portion region.

  Examples of the positive type image forming layer include an interaction release system (thermal positive) image forming layer, a known acid catalyst decomposition system, and an o-quinonediazide compound-containing system. These are soluble in water or alkaline water by the action of the polymer compound that formed the layer being released by the acid or heat energy generated by light irradiation or heating, and are removed by development and non-development. An image portion is formed.

Examples of the negative type image forming layer include known acid-catalyzed cross-linking (including cationic polymerization) image forming layers and polymerization-curing image forming layers. In these compounds, an acid generated by light irradiation or heating serves as a catalyst, and a compound that forms an image forming layer undergoes a crosslinking reaction to be cured to form an image portion, or is polymerizable by radicals generated by light irradiation or heating. The polymerization reaction of the compound proceeds and cures to form an image portion.
The specific hydrophilic layer in the present invention shows an excellent effect even when any of the above image forming layers is formed. However, since the hydrophilicity is improved by contact with an alkaline aqueous solution, Preferably used.
Hereinafter, each image forming layer will be described in detail.

1. Positive type image forming layer As a preferred embodiment of the present invention, an image forming layer containing 50% by mass or more of a novolak-type phenolic resin (hereinafter referred to as a novolak resin as appropriate) and a photothermal conversion agent and capable of being recorded by an infrared laser. A lithographic printing original plate having a provided positive image forming layer can be mentioned. The image forming layer may be a charcoal layer or may have a laminated structure composed of a plurality of image forming layers.

[Novolac type phenolic resin]
First, the novolac type phenol resin will be described. The novolak resin refers to a resin obtained by polycondensation of at least one phenol with at least one of aldehydes or ketones under an acidic catalyst.
Here, examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol, o-ethylphenol, m-ethylphenol, and p-ethylphenol. , Propylphenol, n-butylphenol, tert-butylphenol, 1-naphthol, 2-naphthol, pyrocatechol, resorcinol, hydroquinone, pyrogallol, 1,2,4-benzenetriol, phloroglucinol, 4,4′-biphenyldiol, 2,2-bis (4′-hydroxyphenyl) propane and the like. Examples of the aldehydes include formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, furfural, and the like. Examples of the ketones include acetaldehyde. Ton, methyl ethyl ketone, and methyl isobutyl ketone.

  Preferably, phenols selected from phenol, o-cresol, m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol, resorcinol, and aldehydes selected from formaldehyde, acetaldehyde, propionaldehyde Or a polycondensate with ketones is preferable, and the mixing ratio of m-cresol: p-cresol: 2,5-xylenol: 3,5-xylenol: resorcinol in a molar ratio of 40 to 100: 0 to 50: 0. -20: 0 to 20: 0 to 20 mixed phenols, or (mixed) phenols whose mixing ratio of phenol: m-cresol: p-cresol is 0-100: 0 to 70: 0-60 in molar ratio And a polycondensate of formaldehyde are preferred.

  As these novolak resins, a polystyrene-reduced weight average molecular weight (hereinafter simply referred to as “weight average molecular weight”) measured by gel permeation chromatography is preferably 500 to 20,000, more preferably 1,000 to 15, 000, particularly preferably 3,000 to 12,000. It is preferable for the weight average molecular weight to fall within this range because it is excellent in sufficient film-forming properties and alkali developability in the exposed area.

  When using the said novolak resin as binder resin of an image forming layer, only 1 type may be used and 2 or more types may be used together. Further, all of the binder resins may be the above-mentioned novolak resins, and other resins may be used in combination. Even when other resins are used in combination, the novolak resin is preferably the main binder, and the ratio of the novolak resin in the binder resin component constituting the image forming layer is preferably 50% by mass or more, More preferably, it is in the range of 99.9% by mass.

  As the binder resin that can be used in combination, a commonly used water-insoluble and alkali-soluble alkali-soluble resin having an acidic group in at least one of the main chain and the side chain in the polymer can be used. Phenol resins other than novolak resins, for example, resole resins, polyvinyl phenol resins, acrylic resins having phenolic hydroxyl groups, and the like are also preferably used. Specific examples of the resin that can be used in combination include polymers described in JP-A Nos. 11-44956 and 2003-167343.

[Photothermal conversion agent]
The image forming layer in the invention preferably contains a photothermal conversion agent. The photothermal conversion agent used here can be used without any limitation on the absorption wavelength range as long as it absorbs light energy irradiation and generates heat, but is compatible with readily available high-power lasers. From the above viewpoint, an infrared-absorbing dye or pigment having an absorption maximum at a wavelength of 760 nm to 1200 nm is preferable.

  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, 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, oxonol dyes And dyes such as diimonium dyes, aminium dyes, and croconium dyes.

  Preferred dyes include, for example, cyanine dyes described in JP-A-58-125246, JP-A-59-84356, JP-A-59-202829, JP-A-60-78787, and the like. Methine dyes described in JP-A-58-173696, JP-A-58-181690, JP-A-58-194595, JP-A-58-112793, JP-A-58-224793, JP-A-59- 48187, JP-A 59-73996, JP-A 60-52940, JP-A 60-63744, etc., naphthoquinone dyes, JP-A 58-112792, etc. And cyanine dyes described in British Patent 434,875.

  Also, a near infrared absorption sensitizer described in US Pat. No. 5,156,938 is preferably used, and a substituted arylbenzo (thio) pyrylium salt described in US Pat. No. 3,881,924, Trimethine thiapyrylium salts described in JP-A-57-142645 (US Pat. No. 4,327,169), JP-A-58-181051, 58-220143, 59-41363, 59-84248 Nos. 59-84249, 59-146063, 59-146061, pyranlium compounds, cyanine dyes described in JP-A-59-216146, US Pat. No. 4,283,475 The pentamethine thiopyrylium salts described above and the pyrylium compounds disclosed in Japanese Patent Publication Nos. 5-13514 and 5-19702 are also preferably used. .

  Another example of a preferable dye is a near-infrared absorbing dye described as formulas (I) and (II) in US Pat. No. 4,756,993.

  Particularly preferred among these dyes are cyanine dyes, phthalocyanine dyes, oxonol dyes, squarylium dyes, pyrylium salts, thiopyrylium dyes, and nickel thiolate complexes. Further, the compound described on pages 26-38 of JP-A-2005-99685 is preferable because of its excellent photothermal conversion efficiency, and in particular, the cyanine dye represented by the general formula (a) of JP-A-2005-99685 is the present invention. When used in the photosensitive composition of the invention, it is most preferable because it gives high interaction with the alkali-soluble resin and is excellent in stability and economy.

(Degradable dissolution inhibitor)
In preparing the image forming layer in the image recording of the present invention, a degradable dissolution inhibitor can be further added. In particular, it is possible to use a substance (degradable dissolution inhibitor) that is thermally decomposable, such as an onium salt, an o-quinonediazide compound, and a sulfonic acid alkyl ester, and that substantially reduces the solubility of the alkali-soluble resin when not decomposed. It is preferable from the viewpoint of improving dissolution inhibition of the image area in the developer. As the degradable dissolution inhibitor, onium salts such as sulfonium salts, ammonium salts, diazonium salts, iodonium salts, and o-quinonediazide compounds are preferable, and sulfonium salts, ammonium salts, and diazonium salts are more preferable.

Suitable onium salts for use in the present invention include, for example, U.S. Pat. Nos. 4,069,055, 4,069,056, JP-A-3-140140, JP-A-2006-293162, Ammonium salts described in the specification of JP-A-2004-117546, V. Crivello et al, Polymer J. et al. 17, 73 (1985), J. Am. V. Crivello et al. J. et al. Org. Chem. 43, 3055 (1978); R. Watt et al, J.A. Polymer Sci. , Polymer Chem. Ed. , 22, 1789 (1984), J. Am. V. Crivello et al, Polymer Bull. 14, 279 (1985), J. Am. V. Crivello et al, Macromolecules, 14 (5), 1141 (1981), J. MoI. V. Crivello et al, J.A. Polymer Sci. , Polymer Chem. Ed. 17, 2877 (1979), European Patents 370,693, 233,567, 297,443, 297,442, U.S. Pat. Nos. 4,933,377, 3,902,114 No. 5,041,358, No. 4,491,628, No. 4,760,013, No. 4,734,444, No. 2,833,827, German Patent No. 2,904 Examples thereof include sulfonium salts described in JP-A Nos. 626, 3,604,580, 3,604,581, JP-A 2006-293162, and JP-A 2006-258879.
S. I. Schlesinger, Photogr. Sci. Eng. , 18, 387 (1974), T.A. S. Bal et al, Polymer, 21, 423 (1980), JP-A-5-158230, JP-A-5-158230, general formula (I), JP-A-11-143064, general formula ( 1), and diazonium salts represented by the general formula (1) described in JP-A-11-143064.

  Other preferable onium salts include D.I. C. Necker et al, Macromolecules, 17, 2468 (1984), C.I. S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), U.S. Pat. Nos. 4,069,055 and 4,069,056; V. Crivello et al, Macromolecules, 10 (6), 1307 (1977), Chem. & Eng. News, Nov. 28, p31 (1988), European Patent No. 104,143, US Pat. Nos. 5,041,358, 4,491,628, JP-A-2-150848 and JP-A-2-296514. Iodonium salts, J.M. V. Crivello et al, Macromolecules, 10 (6), 1307 (1977), J. MoI. 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).

  The counter ion of the onium salt includes tetrafluoroboric acid, hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid, 5-nitro-o-toluenesulfonic acid, 5-sulfosalicylic acid, 2,5-dimethylbenzenesulfonic acid, 2,4,6-trimethylbenzenesulfonic acid, 2-nitrobenzenesulfonic acid, 3-chlorobenzenesulfonic acid, 3-bromobenzenesulfonic acid, 2-fluorocaprylnaphthalenesulfonic acid, dodecylbenzenesulfonic acid, 1-naphthol-5-sulfone Examples include acid, 2-methoxy-4-hydroxy-5-benzoyl-benzenesulfonic acid, and paratoluenesulfonic acid. Of these, particularly preferred are alkyl aromatic sulfonic acids such as hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid and 2,5-dimethylbenzenesulfonic acid.

  These onium salts may be used alone or in a plurality of compounds. In addition, when the image forming layer has a laminated structure, it may be added to only a single layer or a plurality of layers, or a compound of a plurality of types may be added separately in layers. Good.

  Suitable quinonediazides include o-quinonediazide compounds. The o-quinonediazide compound used in the present invention is a compound having at least one o-quinonediazide group, which increases alkali solubility by thermal decomposition, and compounds having various structures can be used. That is, o-quinonediazide helps the solubility of the sensitive material system by both the effect of losing the ability to suppress the dissolution of the binder due to thermal decomposition and the change of o-quinonediazide itself into an alkali-soluble substance. Examples of the o-quinonediazide compound used in the present invention include J. The compounds described in pages 339 to 352 of “Light-sensitive systems” by John Coley (John Wiley & Sons. Inc.) can be used, and in particular, o-quinonediazide reacted with various aromatic polyhydroxy compounds or aromatic amino compounds. The sulfonic acid esters or sulfonic acid amides are preferred. Further, benzoquinone (1,2) -diazidosulfonic acid chloride or naphthoquinone- (1,2) -diazide-5-sulfonic acid chloride and pyrogallol-acetone resin as described in JP-B-43-28403 Esters of benzoquinone- (1,2) -diazide sulfonic acid chloride or naphthoquinone- (1,2) -diazide- described in US Pat. Nos. 3,046,120 and 3,188,210 Esters of 5-sulfonic acid chloride and phenol-formaldehyde resin are also preferably used.

  Further, an ester of naphthoquinone- (1,2) -diazido-4-sulfonic acid chloride and phenol formaldehyde resin or cresol-formaldehyde resin, naphthoquinone- (1,2) -diazido-4-sulfonic acid chloride and pyrogallol-acetone resin Similarly, the esters are also preferably used. Other useful o-quinonediazide compounds are reported and known in numerous patents. For example, JP-A-47-5303, JP-A-48-63802, JP-A-48-63803, JP-A-48-96575, JP-A-49-38701, JP-A-48-13354, Japanese Patent Publication Nos. 41-11222, 45-9610, 49-17482, U.S. Pat. Nos. 2,797,213, 3,454,400, and 3,544 No. 323, No. 3,573,917, No. 3,674,495, No. 3,785,825, British Patent No. 1,227,602, No. 1,251,345, No. No. 1,267,005, No. 1,329,888, No. 1,330,932, German Patent No. 854,890 and the like. .

  The amount of the onium salt and / or the o-quinonediazide compound that is a degradable dissolution inhibitor is preferably 0.1 to 10% by mass with respect to the total solid content of the image forming layer according to the present invention. More preferably, it is 0.1-5 mass%, Most preferably, it is the range of 0.2-2 mass%. These compounds can be used alone, but may be used as a mixture of several kinds.

  The amount of additives other than the o-quinonediazide compound is preferably 0 to 5% by mass, more preferably 0 to 2% by mass, and particularly preferably 0.1 to 1.5% by mass. The additive and binder used in the present invention are preferably contained in the same layer.

  Further, a dissolution inhibitor having no decomposability may be used in combination, and preferred dissolution inhibitors include sulfonate esters, phosphate esters, and aromatic carboxylic acids described in detail in JP-A-10-268512. Esters, aromatic disulfones, carboxylic anhydrides, aromatic ketones, aromatic aldehydes, aromatic amines, aromatic ethers, etc., as well as lactone skeletons described in detail in JP-A-11-190903, N, N- Examples thereof include an acid color-forming dye having a diarylamide skeleton and a diarylmethylimino skeleton, which also serves as a colorant, and nonionic surfactants described in detail in JP-A No. 2000-105454.

[Other additives]
Further, in order to enhance image discrimination (hydrophobic / hydrophilic discrimination) and to enhance the resistance to scratches on the surface, carbon described in JP-A-2000-187318 is used. A polymer containing a (meth) acrylate monomer having 2 or 3 perfluoroalkyl groups of 3 to 20 as a polymerization component can be used in combination. The addition amount of such a compound is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, based on the total solid content of the image forming layer according to the present invention.
In the image forming layer according to the present invention, a compound that lowers the static friction coefficient of the surface can be added for the purpose of imparting resistance to scratches. Specific examples include esters of long-chain alkyl carboxylic acids as used in US Pat. No. 6,117,913. The addition amount of such a compound is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, based on the total solid content of the image forming layer.
Further, the image forming layer according to the present invention may contain a compound having a low molecular weight acidic group, if necessary. Examples of acidic groups include sulfonic acid groups, carboxylic acid groups, and phosphoric acid groups. Of these, compounds having a sulfonic acid group are preferred. Specific examples include aromatic sulfonic acids such as p-toluenesulfonic acid and naphthalenesulfonic acid, and aliphatic sulfonic acids.

  In addition, for the purpose of further improving sensitivity, cyclic acid anhydrides, phenols, and organic acids can be used in combination. Examples of cyclic acid anhydrides include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-endooxy-Δ4-tetrahydrophthalic anhydride described in US Pat. No. 4,115,128, Tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, pyromellitic anhydride and the like can be used. As phenols, bisphenol A, p-nitrophenol, p-ethoxyphenol, 2,4,4′-trihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 4-hydroxybenzophenone, 4,4 ′, 4 “-Trihydroxytriphenylmethane, 4,4 ′, 3”, 4 ”-tetrahydroxy-3,5,3 ′, 5′-tetramethyltriphenylmethane and the like. There are sulfonic acids, sulfinic acids, alkylsulfuric acids, phosphonic acids, phosphoric acid esters, carboxylic acids, and the like, which are described in Japanese Laid-Open Patent Publication No. 60-88942 and Japanese Patent Application Laid-Open No. 2-96755. , P-toluenesulfonic acid, dodecylbenzenesulfonic acid, p-toluenesulfinic acid, ethyl sulfate Phenylphosphonic acid, phenylphosphinic acid, phenyl phosphate, diphenyl phosphate, benzoic acid, isophthalic acid, adipic acid, p-toluic acid, 3,4-dimethoxybenzoic acid, phthalic acid, terephthalic acid, 4-cyclohexene-1, Examples include 2-dicarboxylic acid, erucic acid, lauric acid, n-undecanoic acid, ascorbic acid, etc. When the above cyclic acid anhydrides, phenols and organic acids are added to the image forming layer, they occupy the image forming layer. The ratio is preferably 0.05 to 20% by mass, more preferably 0.1 to 15% by mass, and particularly preferably 0.1 to 10% by mass.

  Further, when preparing a coating solution for an image forming layer according to the present invention, it is described in Japanese Patent Application Laid-Open Nos. 62-251740 and 3-208514 in order to broaden the stability of processing with respect to development conditions. Nonionic surfactants, amphoteric surfactants as described in JP-A-59-121044, JP-A-4-13149, siloxane compounds as described in EP950517, A fluorine-containing monomer copolymer as described in JP-A-11-288093 can be added.

Specific examples of the nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan trioleate, stearic acid monoglyceride, polyoxyethylene nonylphenyl ether and the like. Specific examples of the double-sided activator include alkyldi (aminoethyl) glycine, alkylpolyaminoethylglycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine and N-tetradecyl-N, N-betaine. Type (for example, trade name “Amorgen K” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).
The siloxane compound is preferably a block copolymer of dimethylsiloxane and polyalkylene oxide. Specific examples include DBE-224, DBE-621, DBE-712, DBP-732, DBP-534, manufactured by Chisso Corporation. And polyalkylene oxide-modified silicones such as Tego Glide 100 manufactured by Tego, Germany.
The proportion of the nonionic surfactant and amphoteric surfactant in the image forming layer is preferably 0.05 to 15% by mass, more preferably 0.1 to 5% by mass.

A print-out agent for obtaining a visible image immediately after heating by exposure, or a dye or pigment as an image colorant can be added to the image forming layer of the image recording material of the present invention.
Typical examples of the printing-out agent include a combination of a compound that releases an acid by heating by exposure (photoacid releasing agent) and an organic dye that can form a salt. Specifically, combinations of o-naphthoquinonediazide-4-sulfonic acid halides and salt-forming organic dyes described in JP-A-50-36209 and JP-A-53-8128, 36223, 54-74728, 60-3626, 61-143748, 61-151644 and 63-58440, and trihalomethyl compounds and salt-forming organic dyes Can be mentioned. Such trihalomethyl compounds include oxazole-based compounds and triazine-based compounds, both of which have excellent temporal stability and give clear printout images.

  As the image colorant, other dyes can be used in addition to the above-mentioned salt-forming organic dyes. Examples of suitable dyes including salt-forming organic dyes include oil-soluble dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-505 (oriental chemical industry) Manufactured by Co., Ltd.), Victoria Pure Blue, Crystal Violet (CI42555), Methyl Violet (CI42535), Ethyl Violet, Rhodamine B (CI145170B), Malachite Green (CI42000), Methylene Blue (CI522015), and the like. The dyes described in JP-A-62-293247 are particularly preferred. These dyes can be added in a proportion of 0.01 to 10% by mass, preferably 0.1 to 3% by mass, based on the total solid content of the image forming layer. Furthermore, a plasticizer is added to the image forming layer coating solution according to the present invention, if necessary, in order to impart flexibility of the coating film. For example, butylphthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, acrylic acid or methacrylic acid These oligomers and polymers are used.

In addition to these, epoxy compounds, vinyl ethers, phenol compounds having a hydroxymethyl group, phenol compounds having an alkoxymethyl group, and JP-A No. 11-160860 described in JP-A-8-276558. A crosslinkable compound having an alkali dissolution inhibiting action described in the publication can be appropriately added depending on the purpose.
The image forming layer in the image recording material of the present invention obtained as described above is excellent in film formability and film strength, and the exposed area exhibits high alkali solubility upon infrared exposure.

2. Negative type image forming layer 2-1. Polymerized and cured layer As one of the negative type image forming layers, a polymerized and cured layer is exemplified. This polymerization hardened layer contains (A) an infrared absorber, (B) a radical generator (radical polymerization initiator), and a radical polymerizable compound that is cured by causing a polymerization reaction with the generated radical (C), Preferably (D) a binder polymer is contained. The infrared rays absorbed by the infrared absorbent are converted into heat, and the heat generated at this time decomposes a radical polymerization initiator such as an onium salt to generate radicals. The radically polymerizable compound is selected from compounds having at least one ethylenically unsaturated double bond and having at least one terminal ethylenically unsaturated bond, preferably two or more, and polymerizes in a chain manner by the generated radicals. A reaction takes place and cures.

2-2. Acid cross-linked layer Another embodiment of the image forming layer is an acid cross-linked layer. The acid cross-linking layer contains (E) a compound that generates an acid by light or heat (hereinafter referred to as an acid generator) and (F) a compound that cross-links by the generated acid (hereinafter referred to as a cross-linking agent). And (G) an alkali-soluble polymer that can react with a crosslinking agent in the presence of an acid to form a layer containing them. In this acid cross-linking layer, the acid generated by decomposition of the acid generator by light irradiation or heating promotes the action of the cross-linking agent, and a strong cross-linking structure between the cross-linking agents or between the cross-linking agent and the binder polymer As a result, the alkali solubility is lowered and the developer becomes insoluble. At this time, in order to efficiently use the energy of the infrared laser, (A) an infrared absorber is blended in the image forming layer.

[(A) Infrared absorber]
The image forming layer capable of forming an image with an infrared laser contains an infrared absorber. As an infrared absorber, any material that absorbs light energy used for recording and generates heat can be used without any limitation on the absorption wavelength range, but it is compatible with readily available high-power lasers. From the viewpoint, an infrared-absorbing dye or pigment having an absorption maximum at a wavelength of 800 nm to 1200 nm is preferable.

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

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

  Particularly preferred among these dyes are cyanine dyes, squarylium dyes, pyrylium salts, nickel thiolate complexes, and indolenine cyanine dyes. Further, cyanine dyes and indolenine cyanine dyes are preferable, and one particularly preferable example is a cyanine dye represented by the following general formula (A).

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

R ¹ and R ² each independently represent a hydrocarbon group having 1 to 12 carbon atoms. From the storage stability of the image forming layer coating solution, R ¹ and R ² are preferably hydrocarbon groups having 2 or more carbon atoms, and R ¹ and R ² are bonded to each other to form a 5-membered ring. Alternatively, it is particularly preferable that a 6-membered ring is formed.

Ar ¹ and Ar ² may be the same or different and each represents an aromatic hydrocarbon group which may have a substituent. Preferred aromatic hydrocarbon groups include a benzene ring and a naphthalene ring. Moreover, as a preferable substituent, a C12 or less hydrocarbon group, a halogen atom, and a C12 or less alkoxy group are mentioned. Y 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 alkoxy groups having 12 or less carbon atoms, carboxyl groups, and sulfo groups. 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. From the availability of raw materials, a hydrogen atom is preferred. Za ⁻ represents a counter anion. However, Za ⁻ is not necessary when the cyanine dye represented by formula (A) has an anionic substituent in its structure and neutralization of charge is not necessary. Preferred Za ⁻ is a halogen ion, a perchlorate ion, a tetrafluoroborate ion, a hexafluorophosphate ion, and a sulfonate ion, particularly preferably a perchlorate ion, from the storage stability of the image forming layer coating solution. Hexafluorophosphate ions and aryl sulfonate ions.

Specific examples of the cyanine dye represented by formula (A) that can be suitably used in the present invention include those described in paragraph numbers [0017] to [0019] of JP-A No. 2001-133969. Can do.
Further, other particularly preferable examples include specific indolenine cyanine dyes described in Japanese Patent Application Nos. 2001-6326 and 2001-237840 described above.

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

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

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

  The particle diameter of the pigment is preferably in the range of 0.01 μm to 10 μm, preferably in the range of 0.05 μm to 1 μm, from the viewpoint of the stability of the dispersion in the image forming layer coating solution and the uniformity of the image forming layer. It is more preferable that it is in the range of 0.1 μm to 1 μm.

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

  The content of the infrared absorber in the image forming layer is preferably 0.01 to 50% by mass, more preferably 0.1 to 10% by mass, and more preferably 0.5 to 10% by mass relative to the total solid mass of the image forming layer. 10 mass% is most preferable. Within this range, high-sensitivity recording is possible, and high-quality image formation is possible without the occurrence of contamination in non-image areas.

[(B) Compound generating radical]
The radical generator refers to a compound that initiates and accelerates the polymerization of a compound having a polymerizable unsaturated group by generating radicals by energy of light, heat, or both. As a radical generator applicable to the present invention, a known thermal polymerization initiator or a compound having a bond with a small bond dissociation energy can be selected and used. For example, an onium salt, an s having a trihalomethyl group can be used. -Organic halogen compounds such as triazine compounds and oxazole compounds, peroxides, azo polymerization initiators, arylazide compounds, benzophenones, acetophenones, carbonyl compounds such as thioxanthones, metallocene compounds, hexaarylbiimidazole compounds, organic boron Examples thereof include salt compounds and dizulphone compounds.

  In the present invention, particularly preferable radical generators include onium salts, and among them, onium salts represented by the following general formulas (B-1) to (B-3) are preferably used.

In formula (B-1), Ar ¹¹ and Ar ¹² each independently represent an aryl group having 20 or less carbon atoms, which may have a substituent. Preferred substituents when this aryl group has a substituent include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, or a group having 12 or less carbon atoms. An aryloxy group is mentioned. Z ^11- represents an inorganic anion or an organic anion.

In the formula (B-2), Ar ²¹ represents an aryl group having 20 or less carbon atoms which may have a substituent. Preferred examples of the substituent include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, an aryloxy group having 12 or less carbon atoms, and 12 or less carbon atoms. Examples thereof include an alkylamino group, a dialkylamino group having 12 or less carbon atoms, an arylamino group having 12 or less carbon atoms, or a diarylamino group having 12 or less carbon atoms. Z ^21- represents a counter ion having the same ^meaning as Z ^11- .

In formula (B-3), R ³¹ , R ³² and R ³³ may be the same or different and each represents a hydrocarbon group having 20 or less carbon atoms which may have a substituent. Preferable substituents include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, or an aryloxy group having 12 or less carbon atoms. Z ^31- represents a counter ion having the same ^meaning as Z ^11- .
In the general formulas (B-1) to (B-3), Z ¹¹⁻ , Z ²¹⁻ , and Z ³¹⁻ represent an inorganic anion or an organic anion. As the inorganic anion, a halogen ion (F ⁻ , Cl ^{-, Br -, I -)} , perchlorate ion (ClO ₄ ^-), perborate ion (BrO ₄ ^-), tetrafluoroborate ion _{^{(BF 4 -), SbF 6}} -, PF 6 - , and the like As organic anions, organic borate anions, sulfonate ions, phosphonate ions, carboxylate ions, R ⁴⁰ —SO ₃ H ⁻ , R ⁴⁰ —SO ₂ ^— , R ⁴⁰ —SO ₂ S ⁻ , R ⁴⁰ —SO _{2 are used.} N ^{- -Y-R 40} ion ^{(wherein, R 40} is an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, Y is a single bond, -CO -, - SO -, and represented) and the like a..

  In the present invention, specific examples of onium salts that can be suitably used include those described in paragraph numbers [0030] to [0033] of JP-A No. 2001-133696.

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

These onium salts may be used alone or in combination of two or more.
These onium salts may be added in a proportion of 0.1 to 50% by mass, preferably 0.5 to 30% by mass, particularly preferably 1 to 20% by mass, based on the total solid content of the image forming layer coating solution. it can. When the addition amount is in the above range, highly sensitive recording is achieved, and the occurrence of smudges in the non-image area during printing is suppressed.
These onium salts are not necessarily added to the image forming layer, and may be added to another layer provided adjacent to the image forming layer.

[(C) Radical polymerizable compound]
The radically polymerizable compound used in the image forming layer in this embodiment is a radically polymerizable compound having at least one ethylenically unsaturated double bond, and has at least one terminal ethylenically unsaturated bond, preferably two. It is selected from the compounds having the above. Such a compound group is widely known in the industrial field, and can be used without any particular limitation in the present invention. These have chemical forms such as monomers, prepolymers, i.e. dimers, trimers and oligomers, or mixtures thereof and copolymers thereof. Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. In addition, unsaturated carboxylic acid ester having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group, amide and monofunctional or polyfunctional isocyanate, addition reaction product of epoxy, monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, halogen A substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a group or a tosyloxy group with 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 or the like instead of the unsaturated carboxylic acid.

  Specific examples of acrylic acid ester, methacrylic acid ester, itaconic acid ester, crotonic acid ester, isocrotonic acid ester, maleic acid ester, which are radical polymerizable compounds that are esters of aliphatic polyhydric alcohol compounds and unsaturated carboxylic acids, It describes in paragraph number [0037]-[0042] of Unexamined-Japanese-Patent No. 2001-133696, and these are applicable also to this invention.

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

Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like.
Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B-54-21726.

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

Formula (VI)
^{_{CH 2 = C (R 41)}} COOCH 2 CH (R 42) OH
(However, R ⁴¹ and R ⁴² represent H or CH _3. )

  Also, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, JP-B-58-49860, JP-B-56-17654, Urethane compounds having an ethylene oxide skeleton described in JP-B-62-39417 and JP-B-62-39418 are also suitable.

  Furthermore, radical polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 may be used.

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

For these radically polymerizable compounds, the details of how to use them, such as what structure to use, whether they are used alone or in combination, and how much they are added, can be selected according to the performance design of the final recording material. Can be set. For example, it is selected from the following viewpoints. From the viewpoint of sensitivity, a structure having a high unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, in order to increase the strength of the image area, that is, the cured film, those having three or more functionalities are preferable, and compounds having different functional numbers and different polymerizable groups (for example, acrylate ester compounds, methacrylate esters) A method of adjusting both photosensitivity and strength by using a combination of a compound, a styrene compound and the like is also effective. A compound having a large molecular weight or a compound having high hydrophobicity is excellent in sensitivity and film strength, but may not be preferable in terms of development speed and precipitation in a developer. Further, the selection and use method of the radical polymerization compound is also an important factor for the compatibility and dispersibility with other components (for example, binder polymer, initiator, colorant, etc.) in the image forming layer. The compatibility may be improved by using a low-purity compound or using a combination of two or more compounds. In addition, a specific structure may be selected for the purpose of improving the adhesion of the support, overcoat layer and the like. As for the compounding ratio of the radically polymerizable compound in the image forming layer, a larger amount is advantageous in terms of sensitivity. However, when the amount is too large, undesirable phase separation may occur or the manufacturing process due to the adhesiveness of the image forming layer may occur. Problems (for example, transfer of image forming layer components, manufacturing defects due to adhesion) and precipitation from the developer may occur.
From these viewpoints, the preferred blending ratio of the radical polymerizable compound is often 5 to 80% by mass, preferably 20 to 75% by mass, based on the total components of the composition. These may be used alone or in combination of two or more. In addition, the usage of the radical polymerizable compound can be arbitrarily selected from the viewpoint of polymerization inhibition with respect to oxygen, resolution, fogging, refractive index change, surface adhesiveness, etc. Depending on the case, a layer configuration and coating method such as undercoating and overcoating can be performed.

[(D) Binder polymer]
In such an image forming layer, it is preferable to further use a binder polymer from the viewpoint of improving the film properties of the image forming layer, and it is preferable to use a linear organic polymer as the binder. Any such “linear organic polymer” may be used. Preferably, a linear organic polymer that is soluble or swellable in water or weak alkaline water is selected to enable water development or weak alkaline water development. The linear organic polymer is selected and used not only as a film forming agent for forming an image forming layer, but also according to the use as water, weak alkaline water or an organic solvent developer.
For example, when a water-soluble organic polymer is used, water development becomes possible. Examples of such linear organic polymers include radical polymers having a carboxylic acid group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-54-25957. , JP 54-92723, JP 59-53836, JP 59-71048, ie, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer. Examples thereof include a polymer, a crotonic acid copolymer, a maleic acid copolymer, and a partially esterified maleic acid copolymer. Similarly, there is an acidic cellulose derivative having a carboxylic acid group in the side chain. In addition, those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group are useful.
Among these, a (meth) acrylic resin having a benzyl group or an allyl group and a carboxyl group in the side chain is particularly preferable because of its excellent balance of film strength, sensitivity, and developability.

In addition, Japanese Patent Publication No. 7-2004, Japanese Patent Publication No. 7-120041, Japanese Patent Publication No. 7-120042, Japanese Patent Publication No. 8-12424, Japanese Patent Laid-Open No. 63-287944, Japanese Patent Laid-Open No. 63-287947, Japanese Patent Laid-Open No. Urethane-based binder polymers containing acid groups described in No. 271741, JP-A-11-352691 and the like are very excellent in strength, and are advantageous in terms of printing durability and suitability for low exposure.
In addition, polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble linear organic polymer. In order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

The weight average molecular weight of the polymer used in the present invention is preferably 5000 or more, more preferably in the range of 10,000 to 300,000, and the number average molecular weight is preferably 1000 or more, and more preferably 2000 to 2000 The range is 250,000. The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, and more preferably 1.1 to 10.
These polymers may be random polymers, block polymers, graft polymers or the like, but are preferably random polymers.

  The binder polymer used in the present invention may be used alone or in combination. These polymers are added to the image forming layer in a proportion of 20 to 95% by mass, preferably 30 to 90% by mass, based on the total solid content of the image forming layer coating solution. When the addition amount is less than 20% by mass, the strength of the image portion is insufficient when an image is formed. If the amount added exceeds 95% by mass, no image is formed. Moreover, it is preferable that the compound which has an ethylenically unsaturated double bond which can be radically polymerized, and a linear organic polymer shall be 1 / 9-7 / 3 by mass ratio.

Next, the components of the acid cross-linking layer will be described. The infrared absorber used here can be the same as that used in the polymerization curable image forming layer.
The content is preferably 0.01 to 50% by mass, more preferably 0.1 to 10% by mass, and most preferably 0.5 to 10% by mass with respect to the total solid mass of the image forming layer.
In the range of the content, highly sensitive recording can be achieved, and furthermore, the occurrence of stains in the obtained non-image portion for lithographic printing is suppressed.

[(E) Acid generator]
In the present embodiment, an acid generator that generates an acid by being decomposed by heat refers to a compound that generates an acid when irradiated with light in a wavelength region of 200 to 500 nm or heated to 100 ° C. or higher.
Examples of the acid generator include a photoinitiator for photocationic polymerization, a photoinitiator for radical photopolymerization, a photodecolorant for dyes, a photochromic agent, or a known acid generator used for a microresist And the like, and known compounds and mixtures thereof that can generate an acid upon thermal decomposition.
Of the acid generators described above, compounds represented by the following general formulas (E-1) to (E-5) are preferred.

In the general formulas (E-1) to (E-5), R ¹ , R ² , R ^4, and R ⁵ may be the same or different and may have a substituent and have 20 or less carbon atoms. Represents a hydrocarbon group. R ³ represents a halogen atom, an optionally substituted hydrocarbon group having 10 or less carbon atoms or an alkoxy group having 10 or less carbon atoms. Ar ¹ and Ar ² may be the same or different and each represents an aryl group having 20 or less carbon atoms which may have a substituent. R ⁶ represents a divalent hydrocarbon group having 20 or less carbon atoms which may have a substituent. n represents an integer of 0 to 4.
In the above formula, R ¹ , R ² , R ⁴ and R ⁵ are preferably hydrocarbon groups having 1 to 14 carbon atoms.

  The preferable aspect of the acid generator represented by the general formulas (E-1) to (E-5) is described in paragraphs [0197] to [0222] of JP-A No. 2001-142230. It is described in detail as a compound of (V). These compounds can be synthesized, for example, by the method described in JP-A-2-100054 and JP-A-2-100055.

  Examples of the acid generator (E) include onium salts having a halide, sulfonic acid, or the like as a counter ion. Among them, iodonium represented by the following general formulas (E-6) to (E-8): Preferred examples include salts having any structural formula of salts, sulfonium salts and diazonium salts.

In the general formulas (E-6) to (E-8), X ⁻ represents a halide ion, ClO ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , BF ₄ ⁻ or R ⁷ SO ₃ ⁻ , , R ⁷ represents a hydrocarbon group having 20 or less carbon atoms which may have a substituent. Ar ³ and Ar ⁴ each independently represent an aryl group having 20 or less carbon atoms, which may have a substituent. R ⁸ , R ⁹ and R ¹⁰ represent a hydrocarbon group having 18 or less carbon atoms which may have a substituent.
Such onium salts are described as compounds of general formulas (I) to (III) in paragraph numbers [0010] to [0035] of JP-A-10-39509.

The addition amount of the acid generator is preferably 0.01 to 50% by mass, more preferably 0.1 to 25% by mass, and most preferably 0.5 to 20% by mass with respect to the total solid mass of the image forming layer. .
When the addition amount is less than 0.01% by mass, an image may not be obtained. When the addition amount exceeds 50% by mass, the non-image area is smeared during printing when used as a lithographic printing original plate. Sometimes.
The above acid generators may be used alone or in combination of two or more.

[(F) Crosslinking agent]
Next, the crosslinking agent will be described. The following are mentioned as a crosslinking agent.
(I) an aromatic compound substituted with a hydroxymethyl group or an alkoxymethyl group (ii) a compound having an N-hydroxymethyl group, an N-alkoxymethyl group or an N-acyloxymethyl group (iii) an epoxy compound

Hereinafter, the compounds (i) to (iii) will be described in detail.
Examples of the aromatic compound substituted with the hydroxymethyl group or alkoxymethyl group (i) include an aromatic compound or a heterocyclic compound polysubstituted with a hydroxymethyl group, an acetoxymethyl group or an alkoxymethyl group. . However, resinous compounds obtained by condensation polymerization of phenols and aldehydes known as resol resins under basic conditions are also included.
Of the aromatic compounds or heterocyclic compounds poly-substituted with a hydroxymethyl group or an alkoxymethyl group, among them, a compound having a hydroxymethyl group or an alkoxymethyl group at a position adjacent to the hydroxy group is preferable.
Moreover, in the aromatic compound or heterocyclic compound poly-substituted with an alkoxymethyl group, a compound having an alkoxymethyl group having 18 or less carbon atoms is preferable, and is represented by the following general formulas (F-1) to (F-4). More preferred is a compound.

In the general formulas (F-1) to (F-4), L ^{1 to} L ⁸ are each independently a hydroxymethyl group substituted with an alkoxy group having 18 or less carbon atoms such as methoxymethyl or ethoxymethyl, or Represents an alkoxymethyl group.
These crosslinking agents are preferable in that they have high crosslinking efficiency and can improve printing durability.

(Ii) As a compound having an N-hydroxymethyl group, an N-alkoxymethyl group or an N-acyloxymethyl group, European Patent Publication (hereinafter referred to as “EP-A”) No. 0,133,216, West Germany Monomer and oligomer-melamine-formaldehyde condensate and urea-formaldehyde condensate described in Patent Nos. 3,634,671 and 3,711,264, EP-A 0,212,482 And alkoxy-substituted compounds described in the book.
Among these, for example, melamine-formaldehyde derivatives having at least two free N-hydroxymethyl groups, N-alkoxymethyl groups or N-acyloxymethyl groups are preferable, and N-alkoxymethyl derivatives are most preferable.

(Iii) Examples of the epoxy compound include monomers, dimers, oligomers, and polymer epoxy compounds having one or more epoxy groups, such as a reaction product of bisphenol A and epichlorohydrin, a low molecular weight phenol-formaldehyde resin, and the like. Examples include reaction products with epichlorohydrin.
In addition, there can be mentioned epoxy resins described and used in US Pat. No. 4,026,705 and British Patent 1,539,192.

The amount of addition when the compounds (i) to (iii) are used as the crosslinking agent is preferably 5 to 80% by mass, more preferably 10 to 75% by mass, based on the total solid content of the image forming layer. 20-70 mass% is the most preferable.
When the addition amount is less than 5% by mass, the durability of the image forming layer of the resulting image recording material may be reduced, and when it exceeds 80% by mass, stability during storage may be reduced. .

  In the present invention, (iv) a phenol derivative represented by the following general formula (F-5) can also be suitably used as the crosslinking agent.

In the general formula (F-5), Ar ¹ represents an aromatic hydrocarbon ring which may have a substituent, and R ¹ , R ² and R ³ are hydrogen atoms or carbon atoms having 12 or less carbon atoms. Represents a hydrogen group. m represents an integer of 2 to 4, and n represents an integer of 1 to 3.
From the viewpoint of availability of raw materials, the aromatic hydrocarbon ring is preferably a benzene ring, a naphthalene ring or an anthracene ring. As the substituent, a halogen atom, a hydrocarbon group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, an alkylthio group having 12 or less carbon atoms, a cyano group, a nitro group, a trifluoromethyl group, or the like is preferable.
Among the above, Ar ¹ is a benzene ring, naphthalene ring, halogen atom, hydrocarbon group having 6 or less carbon atoms, or 6 or less carbon atoms, which has no substituent, in that sensitivity can be increased. And a benzene ring or a naphthalene ring having, as a substituent, an alkoxy group of 6 or less, an alkylthio group having 6 or less carbon atoms, an alkylcarbamoyl group having 12 or less carbon atoms, or a nitro group.

As the hydrocarbon group represented by R ¹ or R ² , a methyl group is preferable because synthesis is easy. The hydrocarbon group represented by R ³ is preferably a hydrocarbon group having 7 or less carbon atoms such as a methyl group and a benzyl group because of its high sensitivity. Furthermore, m is preferably 2 or 3 and n is preferably 1 or 2 for ease of synthesis.

[(G) Alkali water soluble polymer compound]
Examples of the alkaline water-soluble polymer compound that can be used in the crosslinked layer applicable to the present invention include novolak resins and polymers having a hydroxyaryl group in the side chain. Examples of the novolak resin include resins obtained by condensing phenols and aldehydes under acidic conditions.

Among them, for example, novolak resin obtained from phenol and formaldehyde, novolak resin obtained from m-cresol and formaldehyde, novolak resin obtained from p-cresol and formaldehyde, novolak resin obtained from o-cresol and formaldehyde, octylphenol and formaldehyde Novolak resin obtained, novolak resin obtained from m- / p-mixed cresol and formaldehyde, phenol / cresol (m-, p-, o- or m- / p-, m- / o-, o- / p- A high molecular weight polymer having a high ortho bond ratio obtained by reacting under no pressure using a catalyst and using a novolac resin obtained from formaldehyde and phenol and paraformaldehyde, in a sealed state under high pressure without using a catalyst. Rack resin and the like are preferable.
The novolak resin may be selected from those having a weight average molecular weight of 800 to 300,000 and a number average molecular weight of 400 to 60,000 depending on the purpose.

A polymer having a hydroxyaryl group in the side chain is also preferred, and examples of the hydroxyaryl group in the polymer include an aryl group having one or more OH groups bonded thereto.
Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, and a phenanthrenyl group, and among them, a phenyl group or a naphthyl group is preferable from the viewpoint of availability and physical properties.
Examples of the polymer having a hydroxyaryl group in the side chain that can be used in the present embodiment include any one of the structural units represented by the following general formulas (G-1) to (G-4). The polymer containing can be mentioned. However, the present invention is not limited to these.

In General Formulas (G-1) to (G-4), R ¹¹ represents a hydrogen atom or a methyl group. R ¹² and R ¹³ may be the same or different and each represents a hydrogen atom, a halogen atom, a hydrocarbon group having 10 or less carbon atoms, an alkoxy group having 10 or less carbon atoms, or an aryloxy group having 10 or less carbon atoms. R ¹² and R ¹³ may be bonded and condensed to form a benzene ring or a cyclohexane ring. R ¹⁴ represents a single bond or a divalent hydrocarbon group having 20 or less carbon atoms. R ¹⁵ represents a single bond or a divalent hydrocarbon group having 20 or less carbon atoms. R ¹⁶ represents a single bond or a divalent hydrocarbon group having 10 or less carbon atoms. X ¹ represents a single bond, an ether bond, a thioether bond, an ester bond or an amide bond. p represents an integer of 1 to 4. q and r each independently represents an integer of 0 to 3.

These alkali-soluble polymers are described in detail in paragraph numbers [0130] to [0163] of JP-A No. 2001-142230.
The alkaline water-soluble polymer compound that can be used in this embodiment may be used alone or in combination of two or more.

The addition amount of the alkaline water-soluble polymer compound is preferably 5 to 95% by mass, more preferably 10 to 95% by mass, and most preferably 20 to 90% by mass with respect to the total solid content of the image forming layer.
When the addition amount of the alkali water-soluble resin is less than 5% by mass, the durability of the image forming layer may be deteriorated, and when it exceeds 95% by mass, image formation may not be performed.

  Further, as a known recording material applicable to the image forming layer according to the present invention, a negative type image recording material containing a phenol derivative described in JP-A-8-276558, or described in JP-A-7-306528 is disclosed. Negative recording material containing a diazonium compound, negative type using an acid-catalyzed crosslinking reaction using a polymer having a heterocyclic group having an unsaturated bond in the ring described in JP-A-10-203037 Examples thereof include image forming materials, and the image forming layer described in these materials can be applied to the acid crosslinking layer as the negative image forming layer in the present invention.

[Other ingredients]
In addition to these, various compounds other than these may be further added to such a negative type image forming layer. For example, a dye having a large absorption in the visible light region can be used as an image colorant. In addition, pigments such as phthalocyanine pigments, azo pigments, carbon black, and titanium oxide can also be suitably used.
Further, in the present invention, when the image forming layer is a polymerization hardened layer, in order to prevent unnecessary thermal polymerization of a compound having an ethylenically unsaturated double bond capable of radical polymerization during preparation or storage of a coating solution. It is desirable to add a small amount of a thermal polymerization inhibitor. Suitable thermal polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol ), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxylamine aluminum salt and the like. The addition amount of the thermal polymerization inhibitor is preferably about 0.01% by mass to about 5% by mass with respect to the mass of the entire composition. If necessary, higher fatty acid derivatives such as behenic acid and behenic acid amide may be added to prevent polymerization inhibition due to oxygen and unevenly distributed on the surface of the image forming layer in the drying process after coating. Good. The amount of the higher fatty acid derivative added is preferably about 0.1% by mass to about 10% by mass of the total composition.

Further, in the image forming layer coating solution of the present invention, nonionic surface activity as described in JP-A Nos. 62-251740 and 3-208514 is used in order to broaden the processing stability against development conditions. An amphoteric surfactant as described in JP-A-59-121044 and JP-A-4-13149 can be added.
Specific examples of the nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan trioleate, stearic acid monoglyceride, polyoxyethylene nonylphenyl ether and the like.

Specific examples of amphoteric surfactants include alkyldi (aminoethyl) glycine, alkylpolyaminoethylglycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine, N-tetradecyl-N, N- Examples include betaine type (for example, trade name Amorgen K, manufactured by Dai-ichi Kogyo Co., Ltd.).
The proportion of the nonionic surfactant and amphoteric surfactant in the image forming layer coating solution is preferably 0.05 to 15% by mass, more preferably 0.1 to 5% by mass.

  Furthermore, a plasticizer is added to the image forming layer coating liquid in the present invention as needed to impart flexibility of the coating film. For example, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate and the like are used.

3. Hydrophobized precursor-containing image forming layer As a further image forming layer that can be applied to the lithographic printing plate support of the present invention, a compound capable of forming a hydrophobic region by heating or irradiation with radiation (hereinafter, appropriately hydrophobized precursor) Heat-sensitive image-forming layer containing the body). Such an image-forming layer is fused to each other by heating, such as (a) a fine particle polymer having a heat-reactive functional group, or (b) a microcapsule containing a compound having a heat-reactive functional group. For example, if it is a microcapsule, it contains a compound that forms an image area region, that is, a hydrophobic region (parent ink region) by causing a chemical reaction of the inclusion by heat, and these are preferably Since it is dispersed in a hydrophilic binder, after image formation (exposure), a lithographic printing plate precursor is mounted on a printing machine cylinder, and a dampening solution and / or ink is supplied to perform special development processing. It is characterized in that it can be developed on the machine without performing it.

Such an image forming layer contains (a) a fine particle polymer having a thermoreactive functional group, or (b) a microcapsule encapsulating a compound having a thermoreactive functional group.
Examples of the heat-reactive functional group common to the above (a) and (b) include, for example, an ethylenically unsaturated group (for example, acryloyl group, methacryloyl group, vinyl group, allyl group) that undergoes a polymerization reaction, and an addition reaction. Isocyanate group or block thereof, functional group having an active hydrogen atom that is the reaction partner (for example, amino group, hydroxyl group, carboxyl group), epoxy group that also performs addition reaction, amino group that is the reaction partner, carboxyl group Or a hydroxyl group, the carboxyl group and hydroxyl group or amino group which perform a condensation reaction, the acid anhydride and amino group or hydroxyl group which perform a ring-opening addition reaction are mentioned. The thermoreactive functional group used in the present invention is not limited to these, and may be any functional group that performs any reaction as long as a chemical bond is formed.

[(A) Fine particle polymer having a thermally reactive functional group]
(A) Thermally reactive functional groups suitable for the fine particle polymer include, for example, acryloyl group, methacryloyl group, vinyl group, allyl group, epoxy group, amino group, hydroxyl group, carboxyl group, isocyanate group, and acid anhydride group. And groups protecting them. The introduction of the thermally reactive functional group into the polymer fine particles may be performed at the time of polymerizing the polymer, or may be performed by utilizing a polymer reaction after the polymerization.

When the thermoreactive functional group is introduced during the polymerization of the polymer, it is preferable to perform emulsion polymerization or suspension polymerization using a monomer having a thermoreactive functional group.
Specific examples of the monomer having a heat-reactive functional group include allyl methacrylate, allyl acrylate, vinyl methacrylate, vinyl acrylate, glycidyl methacrylate, glycidyl acrylate, 2-isocyanate ethyl methacrylate, and its blocked alcohol, 2-isocyanate ethyl acrylate. Block isocyanates with alcohol, 2-aminoethyl methacrylate, 2-aminoethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, acrylic acid, methacrylic acid, maleic anhydride, difunctional acrylate, difunctional methacrylate Can be mentioned. The monomer having a heat-reactive functional group used in the present invention is not limited to these.
Examples of the monomer having no thermally reactive functional group that can be copolymerized with these monomers include styrene, alkyl acrylate, alkyl methacrylate, acrylonitrile, and vinyl acetate. The monomer having no heat-reactive functional group used in the present invention is not limited to these.

  Examples of the polymer reaction used when the thermally reactive functional group is introduced after polymerization of the polymer include the polymer reaction described in International Publication No. 96/34316.

Among the above-mentioned (a) fine-particle polymers having a heat-reactive functional group, those in which the fine-particle polymers are easily fused and coalesced by heat are preferable from the viewpoint of image formability, and from the viewpoint of on-press developability. Particularly preferred are those having a hydrophilic surface and being dispersed in water. In addition, the film contact angle (water droplets in the film) when it is prepared by applying only the fine particle polymer and drying at a temperature lower than the solidification temperature is the contact of the film when it is prepared by drying at a temperature higher than the solidification temperature. It is preferable to be lower than the corner (water droplet in the air).
In order to bring the hydrophilicity of the surface of the fine particle polymer into such a preferable state, a hydrophilic polymer or oligomer such as polyvinyl alcohol or polyethylene glycol, or a hydrophilic low molecular weight compound may be adsorbed on the surface of the fine particle polymer. The surface hydrophilization method is not limited to these, and various known surface hydrophilization methods can be applied.

(A) The thermal fusing temperature of the fine particle polymer having a heat-reactive functional group is preferably 70 ° C. or higher, but more preferably 80 ° C. or higher in view of stability over time. However, if the heat fusion temperature is too high, it is not preferable from the viewpoint of sensitivity, so the range of 80 to 250 ° C is preferable, and the range of 100 to 150 ° C is more preferable.
(A) The average particle diameter of the fine particle polymer is preferably 0.01 to 20 μm, more preferably 0.05 to 2.0 μm, and more preferably 0.1 to 1.0 μm. preferable. Within this range, good resolution and stability over time can be obtained.
(A) The addition amount of the fine particle polymer is preferably 50 to 98% by mass, more preferably 60 to 95% by mass, based on the solid content of the image forming layer.

[(B) Microcapsules encapsulating a compound having a thermally reactive functional group]
(B) Thermally reactive functional groups suitable for microcapsules include, for example, polymerizable unsaturated groups, hydroxyl groups, carboxyl groups in addition to the functional groups previously mentioned as common to (a) and (b). , Carboxylate groups, acid anhydride groups, amino groups, epoxy groups, isocyanate groups, isocyanate block bodies, and the like.

  The compound having a polymerizable unsaturated group is preferably a compound having at least one, preferably two or more ethylenically unsaturated bonds such as acryloyl group, methacryloyl group, vinyl group and allyl group. Such a compound group is widely known in the said industrial field | area, and in this invention, these can be used without being specifically limited. In chemical form, these are monomers, prepolymers, ie dimers, trimers and oligomers, or mixtures thereof, and copolymers thereof.

Specific examples include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid), esters thereof, and unsaturated carboxylic acid amides. Of these, esters of unsaturated carboxylic acids and aliphatic polyhydric alcohols and amides of unsaturated carboxylic acids and aliphatic polyvalent amines are preferred.
In addition, an addition reaction product of an unsaturated carboxylic acid ester or unsaturated carboxylic acid amide having a nucleophilic substituent such as a hydroxyl group, amino group, mercapto group and the like with a monofunctional or polyfunctional isocyanate or epoxide, and a monofunctional Alternatively, a dehydration condensation reaction product with a polyfunctional carboxylic acid is also preferably used.
In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, and a halogen group or a tosyloxy group Also suitable are substitution reaction products of unsaturated carboxylic acid esters or amides having a leaving substituent with monofunctional or polyfunctional alcohols, amines or thiols.
Another preferred example is a compound in which the unsaturated carboxylic acid is replaced with unsaturated phosphonic acid or chloromethylstyrene.

  Specific examples of these compounds include the paragraphs [0014] to [0035] of JP-A No. 2001-27742 previously proposed by the applicant of the present invention, and detailed production of microcapsules containing these compounds. The method is described in [0036] to [0039], and these descriptions can also be applied to the present invention.

(B) The microcapsule wall preferably used for the microcapsule has a three-dimensional cross-linking and has a property of swelling with a solvent. From such a viewpoint, the wall material of the microcapsule is preferably polyurea, polyurethane, polyester, polycarbonate, polyamide, or a mixture thereof, and polyurea and polyurethane are particularly preferable. Further, a compound having a thermally reactive functional group may be introduced into the microcapsule wall.
(B) The average particle size of the microcapsules is preferably 0.01 to 20 μm, more preferably 0.05 to 2.0 μm, and particularly preferably 0.10 to 1.0 μm. Within the above range, good resolution and stability over time can be obtained.

(B) In an image forming mechanism using a microcapsule having a heat-reactive functional group, a microcapsule material, a compound encapsulated in the microcapsule material, and another image forming layer in which the microcapsule is dispersed Any component that reacts to form an image area, that is, a hydrophobic area (parent ink area) may be used. For example, a type in which microcapsules are fused together by heat, a microcapsule inclusion Of these, the compound that exudes to the capsule surface or outside the microcapsule at the time of application, or the compound that enters the microcapsule wall from the outside causes a chemical reaction by heat, or the microcapsule material or the encapsulated compound A type that reacts with a hydrophilic resin to which is added, or a low molecular weight compound that has been added, two or more types The microcapsule wall material or its inclusion, by using those to have a functional group such as thermally react with each other in different functional groups each, such as the type of reacting microcapsules each other and the like.
Therefore, although it is preferable for image formation that the microcapsules are fused together by heat, it is not essential.

  (B) The addition amount of the microcapsules to the image forming layer is preferably 10 to 60% by mass, and more preferably 15 to 40% by mass in terms of solid content. Within the above range, good on-press developability as well as good sensitivity and printing durability can be obtained.

(B) When microcapsules are added to the image forming layer, a solvent that dissolves the inclusions and swells the wall material can be added to the microcapsule dispersion medium. By such a solvent, diffusion of the encapsulated compound having a heat-reactive functional group to the outside of the microcapsule is promoted.
Such a solvent depends on the microcapsule dispersion medium, the material of the microcapsule wall, the wall thickness, and the inclusion, but can be easily selected from many commercially available solvents. For example, in the case of water-dispersible microcapsules composed of crosslinked polyurea and polyurethane walls, alcohols, ethers, acetals, esters, ketones, polyhydric alcohols, amides, amines, fatty acids and the like are preferable.

  A solvent that does not dissolve in the microcapsule dispersion but dissolves when the solvent is mixed can also be used. The amount of addition is determined by the combination of materials. When the amount is less than the appropriate value, image formation is insufficient, and when the amount is large, the stability of the dispersion deteriorates. Usually, it is preferably 5 to 95% by mass of the coating solution, more preferably 10 to 90% by mass, and particularly preferably 15 to 85% by mass.

[Other ingredients]
In the heat-sensitive image forming layer in this embodiment, in addition to (a) a fine particle polymer having a heat-reactive functional group having the image-forming property, or (b) a microcapsule encapsulating a compound having a heat-reactive functional group, Various additives can be used in combination depending on the purpose.
(Reaction initiator, reaction accelerator)
In the thermal image forming layer, a compound that initiates or accelerates these reactions may be added as necessary. Examples of the compound that initiates or accelerates the reaction include compounds that generate radicals or cations by heat. Specific examples include lophine dimers, trihalomethyl compounds, peroxides, azo compounds, onium salts including diazonium salts or diphenyliodonium salts, acyl phosphines, and imide sulfonates.
These compounds are preferably added in the range of 1 to 20% by mass of the solid content of the image forming layer, and more preferably in the range of 3 to 10% by mass. If it is within the above range, good onset reaction reaction effect or reaction promoting effect can be obtained without impairing on-press developability.

(Hydrophilic resin)
A hydrophilic resin may be added to such a heat-sensitive image forming layer in the present invention. Addition of the hydrophilic resin not only improves the on-press developability, but also improves the film strength of the thermal image forming layer itself.
As the hydrophilic resin, those having a hydrophilic group such as hydroxyl, carboxyl, hydroxyethyl, hydroxypropyl, amino, aminoethyl, aminopropyl, carboxymethyl and the like are preferable.

Specific examples of hydrophilic resins include gum arabic, casein, gelatin, starch derivatives, carboxymethylcellulose and its sodium salt, cellulose acetate, sodium alginate, vinyl acetate-maleic acid copolymers, styrene-maleic acid copolymers, polyacrylic acids and Salts thereof, polymethacrylic acids and their salts, homopolymers and copolymers of hydroxyethyl methacrylate, homopolymers and copolymers of hydroxyethyl acrylate, homopolymers and copolymers of hydroxypropyl methacrylate, homopolymers and copolymers of hydroxypropyl acrylate, hydroxybutyl Homopolymers and copolymers of methacrylate, homopolymers and copolymers of hydroxybutyl acrylate Homopolymers of limers, polyethylene glycols, hydroxypropylene polymers, polyvinyl alcohols, and hydrolyzed polyvinyl acetate, polyvinyl formal, polyvinyl butyral, polyvinyl pyrrolidone, acrylamide having a degree of hydrolysis of at least 60% by weight, preferably at least 80% by weight And copolymers, methacrylamide homopolymers and polymers, N-methylolacrylamide homopolymers and copolymers, and the like.
The addition amount of the hydrophilic resin to the heat-sensitive image forming layer is preferably 5 to 40% by mass, more preferably 10 to 30% by mass based on the solid content of the image forming layer. Within this range, good on-press developability and film strength can be obtained.

  In order to form an image of such a heat-responsive image forming layer (heat-sensitive image forming layer) by scanning exposure of infrared laser light or the like, (A) an infrared absorber is contained in the image forming layer. A preferable addition amount is preferably 1 to 30% by mass and more preferably 5 to 25% by mass in the total solid content of the image forming layer coating solution. When the content is in the above range, an image forming layer excellent in both sensitivity and image formability is obtained.

  The image forming layer containing a hydrophobizing precursor is prepared by dissolving or dispersing each of the necessary components in a solvent to prepare a coating solution, which is coated on the hydrophilic surface of the support. The solid content concentration of the coating solution is preferably 1 to 50% by mass.

(Other lithographic printing plate precursors)
The present invention can be preferably used for lithographic printing plate precursors other than infrared laser exposure. Hereinafter, examples of the planographic printing plate precursor and the image forming layer other than the infrared laser exposure will be described in detail.

1. Positive type image forming layer Preferable examples of the positive type image forming layer include conventionally known positive type image forming layers [(a) to (b)] shown below.

(A) Conventionally used conventional positive image forming layer comprising naphthoquinonediazide and novolak resin.
(B) A chemically amplified positive image-forming layer comprising a combination of an alkali-soluble compound protected with an acid-decomposable group and an acid generator.

  The above (a) and (b) are both well known in the art, but are more preferably used in combination with the positive type image forming layers ((c) to (f)) shown below. It is.

(C) A laser-sensitive positive image-forming layer containing a sulfonate polymer and an infrared absorber, which can produce a lithographic printing plate that does not require development processing as described in JP-A-10-282672.
(D) Laser sensitivity comprising a carboxylic acid ester polymer and an acid generator or an infrared absorber capable of producing a lithographic printing plate which does not require development processing as described in EP652483 and JP-A-6-502260. Positive image forming layer.
(E) a laser-sensitive positive type comprising an alkali-soluble compound described in JP-A-11-095421 and a substance that is thermally decomposable and substantially reduces the solubility of the alkali-soluble compound in a state where it is not decomposed. Image forming layer.
(F) An alkali development elution positive image forming layer comprising an infrared absorber, a novolak resin, and a dissolution inhibitor, which can produce an alkali development elution type positive lithographic printing plate.

  On the lithographic printing plate support of the present invention, an image forming layer is formed by dissolving a coating liquid component of the desired layer such as the image recording coating liquid in a solvent and coating it, and a lithographic printing plate precursor is produced. can do. In the lithographic printing plate precursor, in addition to the image forming layer, a protective layer, a resin intermediate layer, an undercoat layer, a backcoat layer, and the like can be formed in the same manner depending on the purpose.

Solvents used here include ethylene dichloride, cyclohexanone, methyl ethyl ketone, methanol, ethanol, propanol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-methoxyethyl acetate, 1-methoxy-2-propyl acetate, dimethoxy Ethane, methyl lactate, ethyl lactate, N, N-dimethylacetamide, N, N-dimethylformamide, tetramethylurea, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, γ-butyrolactone, toluene, etc. When the formation layer is used, water or an aqueous solvent such as alcohols can be used, but the present invention is not limited to this, and it may be appropriately selected according to the physical properties of the image formation layer. These solvents are used alone or in combination.
The concentration of the above components (total solid content including additives) in the solvent is preferably 1 to 50% by mass.
The coating amount (solid content) on the support obtained after coating and drying varies depending on the use, but generally 0.5 to 5.0 g / m ² is preferable for the photosensitive printing plate. As the coating amount decreases, the apparent sensitivity increases, but the film properties of the photosensitive film deteriorate.
Various methods can be used as the coating method, and examples thereof include bar coater coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating, and roll coating.

  As described above, the lithographic printing plate precursor obtained using the lithographic printing plate support of the present invention has high hydrophilicity and has a surface having excellent durability, so that after image formation. The printing stain resistance of the non-image area is improved, and a large number of high-quality printed materials can be obtained even under severe printing conditions.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, the scope of the present invention is not limited by these.

[Examples 1 to 9, Comparative Example 1]
-Fabrication of aluminum substrate-
A molten beverage was prepared using a used beverage can (UBC) metal bar having the composition shown in Table 1, and after performing the molten metal treatment and filtration, an ingot having a thickness of 500 mm and a width of 1200 mm was prepared by a DC casting method. After the surface was shaved with a chamfering machine with an average thickness of 10 mm, it was kept soaked at 550 ° C. for about 5 hours, and when the temperature dropped to 400 ° C., rolling with a thickness of 2.7 mm using a hot rolling mill A board was used. Furthermore, heat treatment was performed at 500 ° C. using a continuous annealing machine. Subsequently, cold rolling was performed to finish the sheet to a thickness of 0.3 mm and a width of 1060 mm to obtain aluminum plates AL-1 and AL-2. An aluminum plate AL-3 was obtained by treating the aluminum material having the composition of JIS A 1050 in the same manner as described above. The respective compositions are shown in Table 1. In addition, the unit of the numerical value in a table | surface is the mass%.

<Surface roughening treatment>
Each obtained aluminum plate was subjected to the surface roughening treatment shown below to obtain lithographic printing plate supports P-1 to P-5.
The surface treatment was performed by performing the following treatments (a) to (e) continuously (as described in Table 2).

(A) Mechanical surface roughening treatment using a brush and an abrasive A suspension of pumiston (average particle size 30 μm) having a specific gravity of 1.13 suspended in water is used as a polishing slurry, and one rotating brush is used. Then, mechanical surface roughening was performed at a brush rotational speed of 250 rpm so that Ra after roughening was 0.58 μm.

As the roller-shaped brush, use is made of 6/10 nylon bristles with a bristles length of 50 mm and bristles diameter of 0.295 mm, which are planted so as to be dense by making holes on the surface of a 300 mm diameter stainless steel roller. It was.
As the two supporting rollers under the brush, a stainless steel roller having a diameter of 200 mm was used at a distance of 300 mm between the centers.

  The roller-like brush is pressed with a pressure of 7 kW plus against the load before the brush motor is pressed against the aluminum plate, and the rotation direction on the roughened surface is the conveyance direction of the aluminum web W. It was rotated to be in the same direction.

  The concentration of the abrasive was continuously determined from the temperature and specific gravity of the abrasive slurry, and mechanical surface roughening was performed while replenishing the slurry collection tank with water and pumiston so that the concentration was constant. Further, the pumicestone pulverized and refined in the mechanical surface roughening was removed by a classifier in the particle diameter adjusting unit so that the particle size distribution of the pamiston in the abrasive slurry was substantially constant. A cyclone was used as the classifier.

(B) Etching treatment in alkaline aqueous solution An aluminum plate was sprayed with an aqueous solution having a caustic soda concentration of 370 g / L, an aluminum ion concentration of 100 g / L, and a temperature of 60 ° C. to perform an etching treatment. The etching amount of the surface subjected to the electrochemical roughening after the aluminum plate was 3 g / m ² . Thereafter, the liquid is drained with a nip roller, washed with water using a free-falling curtain-like liquid film, and further sprayed with a spray tube having a structure having spray tips spread in a fan shape at intervals of 80 mm. After washing with water for 2 seconds, the liquid was drained with a nip roller.

(C) Electrochemical roughening treatment An electrochemical roughening treatment was carried out by the method described in JP-A-2005-35034, pages 35 (b) to 36 (h). In the support P-1 in which the electrochemical roughening treatment was performed on the UBC aluminum material, a partial unetched portion was generated, and a uniform surface structure could not be obtained.

(D) Anodizing treatment Anodizing treatment was performed using an anodizing apparatus shown in FIG. 4 of JP-A-2005-35034. As the electrolytic solution, an electrolytic solution (temperature 33 ° C.) in which aluminum sulfate was dissolved in a 170 g / L sulfuric acid aqueous solution to make the aluminum ion concentration 5 g / L was used. The anodizing treatment was performed so that the average current density during the anodic reaction of the aluminum plate (about 16 seconds) was 15 A / dm ² , and the final oxide film amount was 2.4 g / m ² . The time for the aluminum plate to participate in the anodic reaction was 16 seconds.
Thereafter, the liquid was drained with a nip roller, washed with water, and further drained with a nip roller.

(E) Silicate treatment The aluminum plate was immersed in a 2.5% by mass aqueous solution of sodium silicate (liquid temperature 20 ° C.) for 10 seconds. The amount of Si on the surface of the aluminum plate measured with a fluorescent X-ray analyzer was 3.5 mg / m ² . Thereafter, the liquid was drained with a nip roller, washed with water, and further drained with a nip roller. Furthermore, 90 degreeC wind was blown for 10 seconds and it was made to dry.

-Formation of hydrophilic layer-
1. Synthesis of Specific Polymer (1-28) In a 1 L three-necked flask, 17.3 g of acrylamide, 1.5 g of mercaptopropyltrimethoxysilane, 15 g of N- (4-methylphenylsulfonyl) methacrylimide, and 200 ml of 1-methoxy-2-propanol And 216 mg of 216 mg of dimethyl-2,2′-azobis (2-methylpropionate) previously dissolved in 6 ml of 1-methoxy-2-propanol was added under a nitrogen stream at 80 ° C. The mixture was kept at the same temperature with stirring for 4 hours, and then cooled to room temperature. 100 ml of ethanol was added, and the precipitated solid was collected by filtration and washed with water to obtain a hydrophilic polymer. The polymer had a weight average molecular weight of 12,000 by GPC (polyethylene oxide standard). ¹³ C-NMR (DMSO-d ₆ ) Thus, it was confirmed that the polymer had the structure of the exemplified compound (1-28) in which a trimethoxysilyl group (50.0 ppm) was introduced at the terminal. Other polymers of the present invention were synthesized in the same manner.

2. Formation of hydrophilic layer with sol-gel liquid composition on support surface 2-1 Adjustment of coating liquid composition Polymer solution 1 and catalyst liquid 1 were adjusted according to the following compositions, mixed with tetramethoxysilane, and sol-gel liquid composition Object 1 was created. The sol-gel liquid composition 1 was stirred at 20 ° C. for 2 hours. The solvent of the polymer solution 1 was adjusted by adding methanol when the solubility of the polymer in water was low.
<Polymer solution 1>
Specific polymer [Exemplary compound (1-28)] 0.5 g
Triethylamine 30mg
12.6g of water
<Catalyst solution 1>
Ethanol 54.9g
Acetylacetone 2.46g
Tetraethoxytitanium 2.81g
0.44 g of water
<Sol-gel solution composition 1>
Polymer solution 1 13.1 g
Catalyst solution 1 2.9 g
Tetramethoxysilane 1.49g

A coating liquid composition 1 was prepared using the sol-gel liquid composition 1 and the dilution liquid 1 prepared as follows.
<Diluent 1>
74.1g of water
26 g of Snowtex C (20% aqueous dispersion) manufactured by Nissan Chemical Industries, Ltd.
Dioctyl sodium sulfosuccinate (5% aqueous solution) 5.5 g
<Coating liquid composition 1>
Sol-gel composition 1 17.54g
Diluent 1 10.1 g

Thereafter, the coating composition was applied onto an aluminum substrate [the composition and treatment method are as shown in Table 2] so that the coating amount after drying was 0.2 g / m ^2, and 120 ° C. And dried for 10 minutes to form a hydrophilic layer, which was used as a lithographic printing plate support. A coating solution composition was prepared in the same manner for other polymers of the present invention [types shown in Table 4].

3. Evaluation of contact angle The surface contact angle (airborne water droplet) on the obtained support was measured using CA-Z manufactured by Kyowa Interface Science Co., Ltd., and compared with an aluminum substrate not coated with the coating solution composition. The results are shown in Table 3 (unit: degree). Table 3 shows the following.
It can be confirmed that the surface physical properties of the substrate surface are controlled by the polymer of the present invention, and are preferably hydrophilized and exhibit a low contact angle. It can be seen that also in the aluminum supports P-1 to P-4 obtained from low-purity aluminum, the effect of hydrophilization is high. Further, when P-1 and P-2 are compared, the effect of the present invention is high with a substrate that is not subjected to electrolytic surface-roughening treatment. Further, when P-2 and P-3 are compared, silicate treatment is performed. It can be seen that the effect of improving hydrophilicity is particularly high with the prepared substrate.

-Thermal positive lithographic printing plate precursor-
(Formation of image forming layer)
An image forming layer was formed on the lithographic printing plate support obtained as described above by the following method to obtain positive lithographic printing plate precursors of the present invention and Comparative Example 1 (described in Table 4). That is, the following image forming layer coating solution 1 was applied with a bar coater, dried at 130 ° C. for 50 seconds using a TARFAI PERFECT OVEN PH200, and an image forming layer having a coating amount after drying of 1.3 g / m ² ( Lower layer) was provided. Then, the following coating solution 2 for image forming layer was applied with a bar coater, dried at 130 ° C. for 60 seconds with a TARFAI PERFECT OVEN PH200, and an image forming layer having a coating amount after drying of 0.26 / m ² was formed. And an infrared-sensitive lithographic printing plate precursor of Example 1 was obtained.
In Table 4, the comparative sample having “None” in the “Polymer” column does not form a hydrophilic layer by applying the sol-gel coating liquid composition, and is described in Table 2. It shows that the image forming layer was applied on the surface-treated aluminum substrate.

(Positive type image forming layer coating solution 1)
N- (4-aminosulfonylphenyl) methacrylamide /
Acrylonitrile / methyl methacrylate copolymer 1.9 g
(36/34/30% by mass: weight average molecular weight 50000, acid value 2.65)
・ 0.3 g of m / p cresol novolak
(M / p = 6/4, weight average molecular weight 4500, unreacted cresol containing 0.8% by mass)
・ Cyanine dye A (the following structure) 0.13g
・ 4,4′-bishydroxyphenylsulfone 0.13 g
・ Tetrahydrophthalic anhydride 0.19g
・ 0.008 g of p-toluenesulfonic acid
・ 3-methoxy-4-diazodiphenylamine hexafluorophosphate 0.032 g
・ The counter ion of ethyl violet is 6-hydroxy-2-
0.078 g changed to naphthalene sulfonate ion
-Fluorosurfactant (Megafac F780, manufactured by Dainippon Ink & Chemicals, Inc. 30% methyl ethyl ketone) 0.2g
・ Methyl ethyl ketone 16.0g
1-methoxy-2-propanol 8.0g
・ Γ-Butyrolactone 8.0g

(Positive type image forming layer coating solution 2)
・ Phenol / m / p Cresol novolak 0.27g
(Phenol / m / p = 5/3/2 Weight average molecular weight 5000,
Contains 0.8% by mass of unreacted cresol)
・ Acrylic resin B (the following structure) 0.042g
・ Cyanine dye A (the above structure) 0.019 g
・ Long chain alkyl group-containing polymer A 0.042 g
・ Sulphonium salt compound C (the following structure) 0.065g
-Ammonium compound D (the following structure) 0.004 g
-Fluorosurfactant (Megafac F780, Dainippon Ink & Chemicals, Inc. 30% methyl ethyl ketone) 0.02g
・ Fluorosurfactant E (the following structure)
(Methyl ethyl ketone 60%) 0.032 g
・ Methyl ethyl ketone 13.0g
・ 1-methoxy-2-propanol 7.0g

[Synthesis Example 1: (a) Synthesis of long-chain alkyl group-containing polymer A]
A 1000 ml three-necked flask equipped with a condenser and a stirrer was charged with 59 g of 1-methoxy-2-propanol and heated to 80 ° C. Under a nitrogen stream, a solution consisting of 42.0 g of n-stearyl methacrylate, 16.0 g of methacrylic acid, 0.714 g of a polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries), and 59 g of 1-methoxy-2-propanol was used for 2 hours. It was dripped over half. Furthermore, it was made to react at 80 degreeC for 2 hours. The reaction mixture was cooled to room temperature and poured into 1000 ml of water. After decantation, the product was washed with methanol, and the obtained liquid product was dried under reduced pressure to obtain 73.5 g of (a) a long-chain alkyl group-containing polymer A shown below. The mass average molecular weight measured by gel permeation chromatography (GPC) using polystyrene as a standard substance was 66,000.

-Evaluation of lithographic printing plate precursors-
The obtained lithographic printing plate precursor was subjected to power exposure using a TrendSetter 3244VFS manufactured by Creo at a drum rotation speed of 150 rpm and changing the exposure energy. afterwards,. Then, Fujifilm Corporation's automatic processor LP-940H was loaded with Fujifilm Corporation developer DT-2 (diluted 1: 8) and Fujifilm Corporation Finisher FG-1 (1: 1) and developed with a developer temperature of 32 ° C. and a development time of 12 seconds. The electric conductivity of the developer at this time was 43 mS / cm. The developed lithographic printing plate was printed using a printing machine Lithlon 226 manufactured by Komori Corporation.
The film formation of the image forming layer was reduced, the anti-stain property and the anti-stain property were evaluated by the following methods.

(1) Evaluation of printing durability of image portion In the printing evaluation, it was visually evaluated how many sheets could be printed while maintaining a sufficient ink density. The larger this number, the better the printing durability.

(2) Anti-stain property The blanket was visually evaluated after printing with DIC-GEOS (s) red ink on a Mitsubishi diamond F2 printer (Mitsubishi Heavy Industries, Ltd.) and printing 10,000 sheets. .
The anti-smudge property was evaluated in four grades: ◎, ○, Δ, and × from the side where the degree of dirt on the blanket was small.
◎: No dirt at all ○: No dirt can be visually confirmed (to the extent that it can be confirmed with a magnifying glass)
Δ: Partially dirty ×: Completely dirty

(3) Anti-stain anti-stain property In the above anti-stain property evaluation, after printing 10,000 sheets, the plate was allowed to stand for 1 hour, then printing was started again, and the non-image area blanket was visually evaluated. .
In addition, the evaluation criteria for the anti-stain property were the same as the evaluation criteria for the anti-stain property.
(4) Evaluation of film reduction due to development of image area The unexposed lithographic printing plate precursor was then applied to an automatic developing machine LP-940H manufactured by Fuji Film Co., Ltd. and developed solution DT-2 (1: 8) and Fujifilm Co., Ltd. finisher FG-1 (diluted 1: 1) were charged and developed at a developer temperature of 32 ° C. and a development time of 12 seconds. The electric conductivity of the developer at this time was 43 mS / cm.
The optical density of the photosensitive layer before and after development was measured, and the relative density when the density before development was 100% was expressed as a reduction in the developed film.

From the results in Table 4, the following can be understood. The lithographic printing plate precursors of Examples 1 to 9 are examples in which the decrease in the developed film is suppressed, the printing durability, the antifouling property, and the neglected antifouling property are all good, and an aluminum substrate having a relatively low purity is used. It can be seen that the same effects as those in Example 9 using a high-purity aluminum substrate are also exhibited in 1 to 8. Among them, Example 2 and Examples 4 to 8 which were subjected to silicate treatment and were not subjected to electrolytic surface-roughening exhibited particularly excellent performance, and the production process compared to the case where a conventional lithographic printing plate support was used. It can be seen that excellent and unexpected effects can be obtained even if the above is simplified.
On the other hand, the planographic printing plate precursor of Comparative Example 1 in which the hydrophilic layer according to the present invention was not provided is in accordance with the present invention both in terms of printing durability due to adhesion to the substrate and stain resistance. The performance was inferior.

Example 10
The hydrophilic layer and the image forming layer were the same as in Example 1 except that the aluminum support of the lithographic printing plate precursor described in Example 1 was a polyethylene terephthalate film (film thickness 0.3 mm) that was not subjected to roughening treatment. To obtain a planographic printing plate precursor of Example 10. This lithographic printing plate precursor was evaluated in the same manner as in Example 1.
As a result, the printing durability was 100,000 sheets, the developed film was reduced by 100%, the anti-stain property ◎, and the unstained soil property ○, even when using a plastic film support, the same as when using an aluminum support. It was found that the printing performance was excellent.

[Comparative Example 2]
In the adjustment of the coating liquid composition for forming the hydrophilic layer, the same procedure as in Example 1 was conducted except that the specific polymer [Exemplary Compound (1-28)] used in the preparation of the polymer solution 1 was replaced with the following comparative polymer. Thus, a lithographic printing plate precursor of Comparative Example 2 was obtained and evaluated in the same manner as in Example 1.
As a result, both the anti-stain property and the anti-stain property were at a satisfactory level with no practical problem, but the reduction of the developed film was 98%, and the printing durability was 100,000 sheets. From this, by providing a hydrophilic layer formed using the specific polymer of the present invention, not only the surface hydrophilicity but also the adhesion to the substrate and the printing durability resulting therefrom are improved as compared to conventional products. You can see that

[Examples 11 to 15]
-Thermal negative lithographic printing plate precursor-
(Formation of image forming layer)
A negative type image forming layer coating solution having the following composition was prepared, and this image forming layer coating solution was coated on the aluminum support on which the hydrophilic layer used in Examples 1 to 5 was formed. The coating was applied so that the layer coating amount was 1.3 g / m ² and dried to form a thermal negative type image forming layer, and thermal negative lithographic printing plate precursors 11 to 15 were obtained.
<Negative image forming layer coating solution>
Infrared absorber: Cyanine dye A (the above structure) 0.07 g
・ Acid generator [SH-1] (the following structure) 0.3 g
・ Crosslinking agent [KZ-1] (the following structure) 0.5g
・ Alkali-soluble polymer 1.5g
(Marcalinker MS-4P, manufactured by Maruzen Petrochemical Co., Ltd.)
・ Victoria Pure Blue Naphthalenesulfonate 0.035g
(Hokamigaya Chemical Co., Ltd.)
・ Fluorine-based surfactant 0.01g
(Megafuck F-177, manufactured by Dainippon Ink & Chemicals, Inc.)
・ Phthalic anhydride 0.05g
・ Methyl ethyl ketone 12g
・ Methyl alcohol 10g
・ 4g of 1-methoxy-2-propanol
・ 4 g of 3-methoxy-1-propanol

[Exposure and development processing]
The obtained negative planographic printing plate precursors 11 to 15 were subjected to conditions of output 9 W, outer drum rotation speed 210 rpm, plate surface energy 100 mJ / cm ² , resolution 2400 dpi, using a Trend setter 3244VFS manufactured by Creo equipped with a water-cooled 40 W infrared semiconductor laser. And exposed. After the exposure, the film was heated at 288 ° F. for 75 seconds in an oven manufactured by Wisconsin, and then developed using an automatic developing machine LP940H manufactured by Fuji Photo Film Co., Ltd. The negative lithographic printing of Examples 11 to 15 Versions 11-15 were obtained. The developer used was 1: 4 water diluted water of DP-4 made by the company, the temperature of the developing bath was 30 ° C., and the 1: 1 water diluted solution of FP-2W made by the company was used as the finisher.

[Printing and evaluation]
Regarding the negative lithographic printing plates 11 to 15 obtained above, printing is continued under the above conditions, and as in Example 1, how many sheets can be printed while maintaining a sufficient ink density is visually evaluated. And used as an index of printing durability. Further, in the same manner as in Example 1, the antifouling property and the left antifouling property were evaluated.
As a result, the printing durability is in the range of 80,000 to 120,000 sheets, both the anti-stain property and the anti-stain property are ◎-○ rank, and even when the image forming layer is replaced with a thermal negative type. As in the case of the thermal positive type image forming layer, it was confirmed that the development film loss of the image forming layer was suppressed, and that the printing durability, anti-stain property, and anti-stain property were all good.

[Examples 16 to 20]
-Thermal negative (microcapsule) lithographic printing plate precursor-
<Synthesis of Microcapsule (1)>
As an oil phase component, 5 g of xylene diisocyanate adduct (Mitsui Takeda Chemical Co., Ltd., Takenate D-110N), oligomer of 4,4′-diphenylmethane diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., Millionate MR-200) 3.8 g, 4 g of a vinyloxy compound having the following structure, 1.5 g of an infrared absorbing dye [IR-2] having the following structure, and 0.1 g of Pionine A-41-C (manufactured by Takemoto Yushi Co., Ltd.) are dissolved in 18 g of ethyl acetate. did.
As an aqueous phase component, 40 g of a 4% by mass aqueous solution of PVA-205 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 5% tetraethylenepentamine aqueous solution, stirred at room temperature for 30 minutes, and then stirred at 40 ° C. for 3 hours. The microcapsule liquid (1) thus obtained was diluted with distilled water so that the solid content concentration became 20% by mass. The average particle size of the microcapsules was 0.34 μm.

(Formation of image forming layer)
A microcapsule-type image-forming layer coating solution having the following composition was prepared, and the coating amount after drying (image-forming layer coating amount) was 1 on the aluminum support on which the hydrophilic layer used in Examples 1 to 5 was formed. The resultant was applied to 0.0 g / m ² and dried to form a microcapsule type image forming layer, whereby microcapsule type lithographic printing plate precursors 16 to 20 were obtained.
<Microcapsule type image forming layer coating solution>
-25 g of microcapsule solution (1) obtained by the above synthesis
・ 0.5 g of acid precursor with the following structure
・ 75 g of water

[Exposure and development processing]
The obtained microcapsule type lithographic printing plate precursors 16 to 20 are exposed with a Creo Trendsetter 3244VFS equipped with a water-cooled 40 W infrared semiconductor laser under conditions of a plate surface energy of 300 mJ / cm ² and a resolution of 2400 dpi, followed by development processing. Without being attached to a cylinder of a printing machine SOR-M manufactured by Heidelberg, dampening water was supplied, and ink was supplied for printing. A 4% solution of IF-102 manufactured by Fuji Photo Film Co., Ltd. was used as the fountain solution, and Varius ink manufactured by Dainippon Ink & Chemicals, Inc. was used as the ink.

[Printing and evaluation]
For the microcapsule type lithographic printing plates 16 to 20 obtained above, printing was continued after confirming that a good printed matter was obtained under the above conditions, and as in Example 1, how many sheets were sufficient. Whether printing can be performed while maintaining the ink density was evaluated visually and used as an index of printing durability. Further, in the same manner as in Example 1, the antifouling property and the left antifouling property were evaluated.
As a result, the printing durability is in the range of 50,000 to 80,000 sheets, the anti-stain property and anti-stain property are ◎-○ rank, and the image forming layer is replaced with a thermal negative (microcapsule) type. In the same manner as in the thermal positive type image forming layer, the decrease in the developed film was suppressed, and the printing durability, anti-staining property, and anti-stain property were all good.

  As described above, the lithographic printing plate precursor according to the present invention is excellent in all of stain resistance, printing durability, and sensitivity, and it is difficult to produce a lithographic printing plate precursor by a conventional technique as well as a known support. The low-purity aluminum support and the plastic support, which are the above, are excellent in expressing good printing performance.

Claims (11)

Reactivity of at least one of a reactive group capable of being directly chemically bonded to the support surface and a reactive group capable of being chemically bonded to the support surface via a component having a crosslinked structure on the support. And a hydrophilic layer formed by chemically bonding a polymer containing a structural unit (i) and a structural unit (ii) in the following general formula (1) and an image forming layer in this order A lithographic printing plate precursor.

In General Formula (1), R ¹ , R ² , R ³ , and R ⁴ each independently represent a hydrogen atom or a substituent having 1 to 30 carbon atoms, m represents 0, 1 or 2, and L ¹ Represents a single bond or an organic linking group, and Y ¹ has at least a structure selected from —CO—NH—CO—, —CO—NH—SO ₂ —, and —SO ₂ —NH—SO ₂ —. A substituent having 1 to 30 carbon atoms is represented. Here, the polymer containing the structural unit in the general formula (1) is a silane represented by the structural unit (i) at the end of a structure in which a plurality of repeating units represented by the structural unit (ii) are connected. It means a polymer compound having a coupling group. Reactivity of at least one of a reactive group capable of being directly chemically bonded to the support surface and a reactive group capable of being chemically bonded to the support surface via a component having a crosslinked structure on the support. And a hydrophilic layer formed by chemically bonding a polymer containing a structural unit (iii) and a structural unit (iv) in the following general formula (2) and an image forming layer in this order A lithographic printing plate precursor.

In General Formula (2), R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ each independently represent a hydrogen atom or a substituent having 1 to 30 carbon atoms, and n is 0, 1 or 2 L ² represents a single bond or an organic linking group, and Y ² is selected from —CO—NH—CO—, —CO—NH—SO ₂ —, and —SO ₂ —NH—SO ₂ —. Represents a substituent having 1 to 30 carbon atoms and having at least the following structure.   The lithographic printing plate precursor as claimed in claim 1 or 2, wherein the support is an aluminum support.   The lithographic printing plate precursor as claimed in claim 3, wherein the aluminum constituting the aluminum support has a purity of 99.4 to 95% by mass.   The lithographic printing plate precursor as claimed in claim 1 or 2, wherein the support is a plastic film support.   The constituent component having the crosslinked structure has a crosslinked structure formed by hydrolysis and condensation polymerization of an alkoxide compound containing an element selected from Si, Ti, Zr, and Al. Item 6. The lithographic printing plate precursor according to any one of items 5.   The lithographic printing plate precursor as claimed in any one of claims 1 to 6, wherein the image forming layer is recordable with an infrared laser.   The lithographic printing plate precursor as claimed in claim 7, wherein the image forming layer contains an infrared absorber.   The lithographic printing plate precursor as claimed in any one of claims 1 to 8, wherein the image forming layer has a laminate structure of two or more layers.   The lithographic printing plate precursor as claimed in any one of claims 1 to 9, wherein the image forming layer is a positive image forming layer containing a novolac resin.   The lithographic printing plate according to claim 10, wherein the positive-type image forming layer contains an alkali-soluble resin containing 50% by mass or more of a novolak resin with respect to the total alkali-soluble resin, and a sulfonium compound or an ammonium compound. A printing plate master.