JP2012133321A - Direct drawing waterless lithographic printing original plate and manufacturing method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a direct drawing waterless lithographic printing original plate which is highly sensitive and hard to blister, that is, which has wide latitude.SOLUTION: The direct drawing waterless lithographic printing original plate has at least a heat sensitive layer and a silicone rubber layer in this order on a substrate, and has a slope area on the surface of the heat sensitive layer on a side facing the silicone rubber layer, the area ratio of the slope area relative to the surface of the heat sensitive layer being 1 area% or more.

Description

  The present invention relates to a direct-drawing waterless lithographic printing plate precursor and a method for producing the same.

  So far, various printing plates for performing lithographic printing without using dampening water (hereinafter referred to as waterless lithographic printing) using silicone rubber or fluororesin as an ink repellent layer have been proposed. Waterless lithographic printing uses the difference in ink adhesion, with the image area and non-image area on the same plane, the image area being ink-receptive and the non-image area being ink repellent. This is a lithographic printing method in which ink is applied only to the image line area, and then the ink is transferred to a printing medium such as paper, and printing is performed without using dampening water.

  Various exposure methods for waterless planographic printing plate precursors have been proposed. These are broadly classified into a method of irradiating ultraviolet rays through an original film and a computer-to-plate (hereinafter referred to as CTP) method in which an image is directly written from an original without using the original film. Examples of the CTP method include a method of irradiating a laser beam, a method of writing with a thermal head, a method of partially applying a voltage with a pin electrode, and a method of forming an ink repellent layer or an ink receiving layer by inkjet. Among these methods, the method of irradiating laser light is superior to other methods in terms of resolution and plate making speed.

  There are two methods for irradiating laser light: a photon mode method using a photoreaction and a heat mode method in which photothermal conversion is performed to cause a thermal reaction. In particular, the heat mode system has become more useful due to the advantages that it can be handled in a bright room and the rapid progress of semiconductor lasers as light sources.

Various proposals have been made so far for the direct-drawing waterless planographic printing plate precursor corresponding to such a heat mode method. Among these, as a direct-drawing waterless lithographic printing plate precursor that can be made with less laser irradiation energy and has good image reproducibility, a direct-drawing waterless lithographic printing plate precursor having bubbles in the heat-sensitive layer (see, for example, Patent Document 1) ) Has been proposed. In addition, as a method for producing a direct-drawing waterless planographic printing plate precursor that can be made with less laser irradiation energy and has good image reproducibility, a thermosensitive material containing an organic solvent having a solubility parameter of 17.0 (MPa) ^1/2 or less. A method for producing a direct-drawing waterless lithographic printing plate precursor having a step of applying a layer composition solution and a step of drying the thermosensitive layer composition has been proposed (for example, see Patent Document 2).

Japanese Patent Laying-Open No. 2005-300586 (Claims) JP-A-2005-331924 (Claims)

  Direct-drawing waterless lithographic printing plate precursors obtained by the techniques described in Patent Documents 1 and 2 have high sensitivity and can be developed simply by applying a physical force after exposure. However, the highly sensitive direct-drawing waterless lithographic printing plate precursor, in the process of producing a waterless lithographic printing plate, causes a phenomenon called “blistering” in which the silicone rubber layer in the exposed area is lifted, and exposure machine and automatic development In some cases, the silicone rubber layer was transferred to the conveying roller in the machine. The silicone rubber layer transferred to the transport roller may be retransferred to the plate surface of the next plate to be processed, which may cause exposure inhibition or development inhibition.

  SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to solve such problems of the prior art and to provide a direct drawing type waterless lithographic printing plate precursor having high sensitivity and being less susceptible to blistering, that is, having a wide latitude.

  The present invention is a direct-drawing waterless lithographic printing plate precursor having at least a heat-sensitive layer and a silicone rubber layer in this order on a substrate, having an inclined region on the surface of the heat-sensitive layer facing the silicone rubber layer, and A direct-drawing waterless lithographic printing plate precursor, wherein the area ratio of the inclined region to the surface of the heat-sensitive layer is 1% by area or more.

  According to the present invention, it is possible to obtain a direct-drawing waterless lithographic printing plate precursor having high sensitivity and excellent blister resistance and a wide latitude.

  The direct-drawing waterless lithographic printing plate precursor according to the present invention is a direct-drawing waterless lithographic printing plate precursor having at least a heat-sensitive layer and a silicone rubber layer in this order on a substrate, the heat-sensitive layer on the side facing the silicone rubber layer The surface area has an inclined region, and the area ratio of the inclined region to the surface of the heat-sensitive layer is 1 area% or more. Here, the waterless lithographic printing plate precursor refers to a lithographic printing plate precursor that can be printed without using a fountain solution. Waterless planographic printing plate precursor that can directly write images.

The direct-drawing waterless planographic printing plate precursor of the present invention will be described below.
The direct-drawing waterless planographic printing plate precursor of the present invention has at least a heat-sensitive layer and a silicone rubber layer in this order on a substrate.

  As the substrate, known dimensionally stable paper, metal, glass, film, etc., which have been conventionally used as a printing plate substrate, can be used. Specifically, paper, paper laminated with plastic (polyethylene, polypropylene, polystyrene, etc.), aluminum (including aluminum alloy), zinc, copper and other metal plates, soda lime, quartz and other glass plates, silicon wafers, Examples thereof include plastic films such as cellulose acetate, polyethylene terephthalate, polyethylene, polyester, polyamide, polyimide, polystyrene, polypropylene, polycarbonate, and polyvinyl acetal, and paper or plastic film on which the above metal is laminated or vapor-deposited. The plastic film may be transparent or opaque. From the viewpoint of plate inspection, an opaque film is preferable.

Of these substrates, an aluminum plate is particularly preferable because it is dimensionally stable and inexpensive. A polyethylene terephthalate film is particularly preferable as a flexible substrate for light printing.
The thickness of the substrate is not particularly limited, and a thickness corresponding to a printing machine used for lithographic printing may be selected.
Next, the thermosensitive layer that can be preferably used in the present invention will be described. As the heat-sensitive layer, a layer whose physical properties are changed by laser drawing and / or a layer whose adhesive force with the silicone rubber layer is lowered by laser drawing is preferable. For example, a layer obtained by applying a composition containing an active hydrogen-containing polymer, a crosslinking agent and a photothermal conversion substance, or a polymer containing an active hydrogen, an organic complex compound and a photothermal conversion substance, and drying (heating) Can be mentioned.

  The present invention is characterized in that the surface of the heat-sensitive layer facing the silicone rubber layer has an inclined region, and the area ratio of the inclined region to the surface of the heat-sensitive layer is 1 area% or more. The highly sensitive direct-drawing waterless lithographic printing plate precursor as described in Patent Documents 1 and 2 can be developed simply by applying a physical force after exposure. For this reason, in the process of producing a waterless lithographic printing plate, a phenomenon called “fire blistering” occurs in which the silicone rubber layer of the exposed portion is lifted, and exposure is performed when transporting the directly drawn waterless lithographic printing plate precursor after exposure. In some cases, a silicone rubber layer is transferred to a transport roller in a machine or an automatic processor. The silicone rubber layer transferred to the transport roller is retransferred to the plate surface of the next plate to be processed, which causes exposure inhibition and development inhibition. This blistering phenomenon becomes more pronounced as the direct-drawing waterless lithographic printing plate precursor has higher sensitivity and as the exposure amount increases. The direct-drawing waterless lithographic printing plate precursor of the present invention has an inclined region on the surface of the heat-sensitive layer facing the silicone rubber layer, and the area ratio of the inclined region to the surface of the heat-sensitive layer is 1% by area or more. As a result, the sensitivity of the heat-sensitive layer can be locally lowered to maintain the adhesive force with the silicone rubber layer, and the blistering phenomenon can be suppressed. That is, the blister resistance is improved.

In the present invention, the inclined region refers to a planar region that has a gradient of 10 degrees or more, constitutes a raised structure, a depressed structure, or a composite structure of a raised structure and a depressed structure, and is continuous at least partially. The term “gradient” as used herein refers to the angle formed by the inclined region of the surface of the heat-sensitive layer on the side facing the silicone rubber layer and the substrate surface, and is the elevation angle or depression angle. Here, the substrate surface refers to a surface located on one side in the thickness direction of the substrate. On the other hand, the non-inclined region refers to a flat planar region that does not include any of a raised structure, a depressed structure, or a combined structure of a raised structure and a depressed structure, and is a region parallel to the substrate surface. When magnifying and observing an arbitrary part, it is in the vicinity of a raised structure, a depressed structure, a combined structure of a raised structure and a depressed structure, and in an uninclined region selected to have an area of 10 μm ² . If a plane connecting the average heights of the surfaces belonging to some regions is a representative surface of the non-inclined region, the gradient is equal to the angle formed by the inclined region and the representative surface of the non-inclined region.

  Examples of the raised structure include a hemispherical structure, a columnar structure, a cone structure, and a frustum structure. Further, a raised structure that is continuous in a bowl shape may be used. Among these, a frustum structure is preferable from the viewpoint of controllability of the gradient and formability, and a frustum structure is more preferable.

  Examples of the depressed structure include a hemispherical structure, a columnar structure, a cone structure, and a frustum structure. Further, a depressed structure that is continuous in a groove shape may be used. Among these, a frustum structure is preferable from the viewpoint of controllability of the gradient and formability, and a frustum structure is more preferable.

  As a composite structure of the raised structure and the depressed structure, for example, a structure in which the raised structure and the depressed structure are combined can be cited.

  The inclined region may be a curved surface, a flat surface, a smooth surface, or a surface including minute irregularities that do not become an inclined region. From the viewpoint of further improving the blister resistance, the inclined region preferably includes a curved surface, and more preferably a region that forms part of the side surface of the truncated cone structure.

  The inclined region of the heat sensitive layer can be confirmed by observing the vertical cross section of the heat sensitive layer using an electron microscope. In addition, the three-dimensional shape of the inclined region is obtained by observing a horizontal section of a direct-drawing waterless lithographic printing plate precursor obtained by a continuous (ultra-thin) section method using a transmission electron microscope (TEM). Quantitative observation is possible by analyzing the obtained 3D information with existing 3D display / analysis software.

  The in-plane distribution of the inclined region is non-inclined even when the region divided by the non-inclined region is uniformly or non-uniformly or regularly or irregularly formed in the heat-sensitive layer (dot pattern distribution). A distribution in which at least a portion of the region is thinly divided without being divided by the region is uniformly or non-uniformly or regularly or irregularly formed in the heat-sensitive layer (stripe pattern distribution, lattice distribution, net-like) Distribution).

  A projected figure obtained by projecting the inclined area onto a plane parallel to the substrate surface is defined as a horizontal projected figure of the inclined area. For example, if the inclined region is a partial surface of the hemispherical raised structure, the horizontal projection figure is a ring formed by projecting the portion excluding the region of less than 10 degrees near the top of the hemisphere from above. The ratio of the total area of the horizontal projection figure of the inclined area to the area of the horizontal projection figure of the entire surface of the thermal layer projected on the plane parallel to the substrate surface is the heat sensitivity of the inclined area. The area ratio relative to the surface of the layer. The area ratio is 1 area% or more, and preferably 2 area% or more. If it is less than 1 area%, the effect of improving the blister resistance cannot be obtained. If it is 2 area% or more, a blistering resistance will improve more. On the other hand, 30 area% or less is preferable and 20 area% or less is more preferable. If it is 30 area% or less, a sensitivity can be maintained higher. The area ratio of the inclined region to the surface of the heat-sensitive layer is determined by observing the horizontal section of the direct-drawing waterless lithographic printing plate precursor obtained by the continuous (ultra-thin) section method using TEM, and obtaining the obtained three-dimensional information. It is calculated by analyzing with existing 3D display / analysis software. In addition, by observing an arbitrary cross section if the dot pattern is isotropically distributed, by observing an arbitrary cross section perpendicular to the direction if the stripe pattern has a one-dimensional directionality. It is possible to calculate the area ratio instead of observing the continuous horizontal section by the continuous (ultra-thin) section method. Furthermore, when the upper layer of the heat-sensitive layer is transparent and can sufficiently transmit laser light, the inclined region can be observed by laser microscope observation. It is also possible to peel off the upper layer of the heat sensitive layer such as a silicone rubber layer and directly observe the surface of the heat sensitive layer with a laser microscope.

  In the inclined region, the area ratio of the inclined region having a gradient of 20 to 80 degrees is preferably 60 area% or more, more preferably 80 area% or more of the entire inclined region. If it is 60 area% or more, a blister resistance will improve more.

If inclined region is such dot pattern distribution, the area of the inclined region one horizontal projected figure is preferably 0.03 .mu.m ² or more, 0.1 [mu] m ² or more is more preferable. If it is 0.03 μm ² or more, the blister resistance is further improved. On the other hand, the area of the horizontal projection figure in the inclined region is preferably 20 μm ² or less, and more preferably 10 μm ² or less. If it is 20 μm ² or less, the sensitivity can be maintained higher.

As another index of the size of the inclined area, when the diameter of a circle inscribed with respect to the outer boundary line of one horizontal projected figure is defined as the shortest distance, when the inclined area is a stripe pattern distribution, The shortest distance is preferably 0.2 μm or more, and more preferably 0.3 μm or more. If it is 0.2 μm or more, the blister resistance is further improved. On the other hand, the shortest distance is preferably 5.0 μm or less, and more preferably 3.0 μm or less. If it is 5.0 micrometers or less, a sensitivity can be maintained higher.
In the present invention, the polymer having a preferably active hydrogen used in the heat-sensitive layer, for _{example, -OH, -SH, -NH 2,} -NH -, - CO-NH 2, -CO-NH -, - OC (= O) -NH -, - NH- CO-NH -, - CO-OH, -CS-OH, -CO-SH, -CS-SH, -SO 3 H, -PO 3 H 2, -SO 2 -NH ₂ , a polymer having a structural unit having active hydrogen, such as —SO ₂ —NH— or —CO—CH ₂ —CO—. Examples of the polymer having such a structural unit include a homopolymer or copolymer of a monomer containing a carboxyl group such as (meth) acrylic acid, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate. Homopolymers or copolymers of (meth) acrylic acid esters containing hydroxyl groups such as N-alkyl (meth) acrylamide, homopolymers or copolymers of (meth) acrylamide, amines and (meth) acrylic acid A homopolymer or copolymer of an ethylenically unsaturated monomer having active hydrogen such as a homopolymer or copolymer of a reaction product with glycidyl or allyl glycidyl, a homopolymer or copolymer of p-hydroxystyrene or vinyl alcohol Combined (active hydrogen Other ethylenically unsaturated monomers may be used, and ethylenically unsaturated monomers containing no active hydrogen may be used.), Polyurethanes, polyureas, polyamides (nylon resins), epoxy resins, polyalkyleneimines, novolaks Examples thereof include condensates having a structural unit having active hydrogen in the main chain, such as resins, resol resins, and cellulose derivatives. Two or more of these may be contained.

  Among them, a polymer having an alcoholic hydroxyl group, a phenolic hydroxyl group, or a carboxyl group is preferable, and a polymer having a phenolic hydroxyl group (a homopolymer or copolymer of p-hydroxystyrene, a novolac resin, a resole resin, etc.) is more preferable. A resin is more preferable. Examples of novolak resins include phenol novolac resins and cresol novolac resins.

  The content of the polymer having active hydrogen is preferably 20% by weight to 95% by weight, more preferably 50% by weight to 90% by weight, based on the total solid content of the heat-sensitive layer.

  It is also preferable to contain a polymer having active hydrogen and a film-forming polymer that does not have active hydrogen (referred to as another polymer). Other polymers include homopolymers or copolymers of (meth) acrylic acid esters such as polymethyl (meth) acrylate and polybutyl (meth) acrylate, homopolymers of styrene monomers such as polystyrene and α-methylstyrene, or Copolymers, various synthetic rubbers such as isoprene and styrene-butadiene, homopolymers such as vinyl esters such as polyvinyl acetate, copolymers such as vinyl acetate-vinyl chloride, various condensation polymers such as polyester and polycarbonate, etc. Is mentioned.

  The content of these other polymers is preferably 50% by weight or less, more preferably 30% by weight or less, and still more preferably 10% by weight or less in the total solid content of the heat-sensitive layer.

  Examples of the crosslinking agent include known polyfunctional compounds having crosslinkability. For example, polyfunctional isocyanate, polyfunctional blocked isocyanate, polyfunctional epoxy compound, polyfunctional (meth) acrylate compound, polyfunctional aldehyde, polyfunctional mercapto compound, polyfunctional alkoxysilyl compound, polyfunctional amine compound, polyfunctional carboxylic acid, A polyfunctional vinyl compound, a polyfunctional diazonium salt, a polyfunctional azide compound, hydrazine, etc. are mentioned.

  The organic complex compound is composed of a metal and an organic compound, and functions as a crosslinking agent for a polymer having active hydrogen and / or as a catalyst for a thermosetting reaction. Even when the organic complex compound functions as a cross-linking agent, the heat-sensitive layer may further contain the above-described cross-linking agent.

  Examples of the organic complex compound in the present invention include an organic complex salt in which an organic ligand is coordinated to a metal, an organic inorganic complex salt in which an organic ligand and an inorganic ligand are coordinated to a metal, and a metal and an organic molecule through oxygen. Examples thereof include metal alkoxides that are covalently bonded. Among these, the metal chelate compound in which the ligand has two or more donor atoms and forms a ring containing a metal atom, the stability of the organic complex compound itself, the stability of the thermosensitive layer composition solution, etc. It is preferably used from the aspect of.

  The main metals forming the organic complex compounds are Al (III), Ti (IV), Mn (II), Mn (III), Fe (II), Fe (III), Co (II), Co (III ), Ni (II), Ni (IV), Cu (I), Cu (II), Zn (II), Ge, In, Sn (II), Sn (IV), Zr (IV), Hf (IV) Is preferred. Al (III) is particularly preferable from the viewpoint that the effect of improving the sensitivity is easily obtained, and Ti (IV) is particularly preferable from the viewpoint that resistance to the printing ink and the ink cleaning agent is easily exhibited.

Moreover, as a ligand, the compound which has a coordination group which has oxygen, nitrogen, sulfur, etc. as a donor atom is mentioned. Specific examples of the coordinating group include oxygen as a donor atom: -OH (alcohol, enol and phenol), -COOH (carboxylic acid),> C = O (aldehyde, ketone, quinone), -O - (ether), - COOR (ester, R: represents an aliphatic or aromatic hydrocarbon), - N = O (nitroso compounds), - NO ₂ (nitro compound),> NO (N-oxide), Examples of —SO ₃ H (sulfonic acid) and —PO ₃ H ₂ (phosphorous acid) that use nitrogen as a donor atom include —NH ₂ (primary amine, amide, hydrazine),> NH (secondary amine). , hydrazine),> N- (3 amine), - N = N- (azo compounds, heterocyclic compounds), = N-OH (oxime), - NO ₂ (nitro compound), - N = O (nitroso compounds ),> C = N- ( Examples of compounds having sulfur as a donor atom, such as Cuff base, heterocyclic compound),> C = NH (aldehyde, ketone imine, enamines), -NCS (isothiocyanato), -SH (thiol), -S- (thioether) ),> C = S (thioketone, thioamide), = S- (heterocyclic compound), -C (= O) -SH, -C (= S) -OH, -C (= S) -SH (thiocarboxylic acid) ), -SCN (thiocyanato) and the like.

  Among the organic complex compounds formed from the above metals and ligands, the compounds preferably used include Al (III), Ti (IV), Fe (II), Fe (III), and Mn (III). , Co (II), Co (III), Ni (II), Ni (IV), Cu (I), Cu (II), Zn (II), Ge, In, Sn (II), Sn (IV), Zr (IV), Hf (IV) and other metal β-diketones, amines, alcohols, complex compounds with carboxylic acids, and Al (III), Fe (II), Fe (III) Ti (IV), acetylacetone complex of Zr (IV), acetoacetate complex and the like are particularly preferable complex compounds.

  Specific examples of such compounds include the following compounds. Aluminum tris (acetylacetonate), aluminum tris (ethyl acetoacetate), aluminum tris (propyl acetoacetate), aluminum tris (butyl acetoacetate), aluminum tris (hexyl acetoacetate), aluminum tris (nonyl acetoacetate), aluminum tris (Hexafluoropentadionate), aluminum tris (2,2,6,6-tetramethyl-3,5-heptanedionate), aluminum bis (ethyl acetoacetate) mono (acetylacetonate), aluminum bis (acetylacetate) Nate) mono (ethyl acetoacetate), aluminum bis (propyl acetoacetate) mono (acetylacetonate), aluminum bis (butyl acetoacetate) G) Mono (acetylacetonate), aluminum bis (hexyl acetoacetate) mono (acetylacetonate), aluminum bis (propyl acetoacetate) mono (ethyl acetoacetate), aluminum bis (butyl acetoacetate) mono (ethyl acetoacetate) Aluminum bis (hexyl acetoacetate) mono (ethyl acetoacetate), Aluminum bis (nonyl acetoacetate) mono (ethyl acetoacetate), Aluminum dibutoxide mono (acetylacetonate), Aluminum diisopropoxide mono (acetylacetonate) Aluminum diisopropoxide mono (ethyl acetoacetate), aluminum-s-butoxide bis (ethyl acetoacetate), aluminum di-s- Tokishidomono (ethylacetoacetate), aluminum di-isopropoxide mono (9-octadecenyl acetoacetate), etc.. Titanium triisopropoxide mono (allyl acetoacetate), titanium diisopropoxide bis (triethanolamine), titanium di-n-butoxide bis (triethanolamine), titanium diisopropoxide bis (acetylacetonate), titanium Di-n-butoxide bis (acetylacetonate), titanium diisopropoxide bis (2,2,6,6-tetramethyl-3,5-heptanedionate), titanium diisopropoxide bis (ethyl acetoacetate) Titanium di-n-butoxide bis (ethyl acetoacetate), titanium tri-n-butoxide mono (ethyl acetoacetate), titanium triisopropoxide mono (methacryloxyethyl acetoacetate), titanium oxide Dobisu (acetylacetonate), titanium tetra (2-ethyl-3-hydroxyhexyl oxide), titanium dihydroxy bis (lactate), and titanium (ethylene glycolate) bis (dioctyl phosphate). Zirconium di-n-butoxide bis (acetylacetonate), zirconium tetrakis (hexafluoropentanedionate), zirconium tetrakis (trifluoropentanedionate), zirconium tri-n-propoxide mono (methacryloxyethylacetoacetate), zirconium Tetrakis (acetylacetonate), zirconium tetrakis (2,2,6,6-tetramethyl-3,5-heptanedionate), triglycolate zirconate, trilactate zirconate and the like. Iron (III) acetylacetonate, dibenzoylmethane iron (II), tropolone iron, tristroporono iron (III), hinokitiol iron, tris hinokitioro iron (III), acetoacetate iron (III), iron (III) benzoyl Acetonate, iron (III) diphenylpropane dionate, iron (III) tetramethylheptane dionate, iron (III) trifluoropentane dionate, etc. Two or more of these may be contained.

  The content of such an organic complex compound is preferably 0.5 to 50% by weight, more preferably 3 to 30% by weight, based on the total solid content of the heat-sensitive layer. By making the content of the organic complex compound 0.5% by weight or more, the above effects can be further enhanced. On the other hand, when the content is 50% by weight or less, high printing durability of the printing plate can be maintained.

  The photothermal conversion substance is not particularly limited as long as it absorbs laser light, and pigments and dyes that absorb infrared rays or near infrared rays are preferable. For example, black pigments such as carbon black, carbon graphite, aniline black, cyanine black, phthalocyanine, naphthalocyanine-based green pigment, crystal water-containing inorganic compounds, iron, copper, chromium, bismuth, magnesium, aluminum, titanium, zirconium, cobalt Metal powders such as vanadium, manganese, and tungsten, or sulfides, hydroxides, silicates, sulfates, phosphates, diamine compound complexes, dithiol compound complexes, phenolthiol compound complexes, mercaptophenol compound complexes of these metals, etc. Can be mentioned.

  In addition, as dyes that absorb infrared rays or near infrared rays, they are dyes for electronics and recording, and cyanine dyes, azurenium dyes, squarylium dyes, croconium dyes, azo dyes having a maximum absorption wavelength in the range of 700 nm to 1500 nm. Disperse dyes, bisazostilbene dyes, naphthoquinone dyes, anthraquinone dyes, perylene dyes, phthalocyanine dyes, naphthalocyanine metal complex dyes, polymethine dyes, dithiol nickel complex dyes, indoaniline metal complex dyes, molecules Intercalated CT dyes, benzothiopyran spiropyrans, nigrosine dyes and the like are preferably used.

Among these dyes, those having a large molar absorbance coefficient ε are preferably used. Specifically, ε is preferably 1 × 10 ⁴ or more, more preferably 1 × 10 ⁵ or more. If ε is 1 × 10 ⁴ or more, the initial sensitivity can be further improved.

  You may contain 2 or more types of these photothermal conversion substances. By containing two or more kinds of photothermal conversion substances having different absorption wavelengths, it is possible to cope with two or more kinds of lasers having different emission wavelengths.

  Among these, carbon black, dyes that absorb infrared rays or near infrared rays are preferable from the viewpoint of photothermal conversion, economic efficiency, and handleability.

  The content of these photothermal conversion substances is preferably 0.1 to 70% by weight, more preferably 0.5 to 40% by weight, based on the total solid content of the heat-sensitive layer. By making the content of the photothermal conversion substance 0.1% by weight or more, the sensitivity to laser light can be further improved. On the other hand, the high printing durability of a printing plate can be maintained by setting it as 70 weight% or less.

  In the direct-drawing waterless planographic printing plate precursor of the present invention, the heat-sensitive layer may contain various additives as necessary. For example, a silicone surfactant or a fluorine surfactant may be contained in order to improve the coating property. Further, a silane coupling agent, a titanium coupling agent, or the like may be contained in order to enhance the adhesiveness with the silicone rubber layer. The content of these additives varies depending on the purpose of use, but is generally 0.1 to 30% by weight in the total solid content of the heat-sensitive layer.

  For the purpose of increasing sensitivity, the direct-drawing waterless lithographic printing plate precursor of the present invention may have bubbles in the heat-sensitive layer. Examples of the method for forming bubbles in the heat-sensitive layer include the methods described in JP-A-2005-300586 and JP-A-2005-331924.

  Furthermore, for the purpose of maintaining high sensitivity even after lapse of time in addition to high sensitivity immediately after the original plate is produced, the direct-drawing waterless lithographic printing plate precursor of the present invention may have liquid bubbles in the heat-sensitive layer. . The heat-sensitive layer preferably has a liquid bubble containing a liquid having a boiling point in the range of 210 to 270 ° C., whereby a direct-drawing waterless lithographic printing plate precursor capable of maintaining high sensitivity for a long period of time can be obtained. it can. That is, by including a liquid having a boiling point of 210 ° C. or higher, it is easy to maintain the form as a liquid bubble for a long period of time, and high sensitivity can be maintained for a long period of time. On the other hand, by including a liquid having a boiling point of 270 ° C. or lower, the initial sensitivity can be further increased, and the bleeding of the liquid to the surface of the heat-sensitive layer and the peeling of the silicone rubber layer during development are suppressed. Can do. The direct-drawing waterless lithographic printing plate precursor having such a liquid bubble in the heat-sensitive layer has a high initial sensitivity and a high sensitivity after the lapse of time, and thus tends to cause blistering. The present invention is particularly effective for such a highly sensitive original.

  In the present invention, the boiling point of the liquid refers to the boiling point under atmospheric pressure. In addition, when the liquid bubble includes two or more kinds of liquids, the ratio of the liquid having a boiling point in the range of 210 to 270 ° C. is preferably 60% by weight or more, and 80% by weight or more. More preferably, it is 90% by weight or more, and further preferably 100% by weight.

  The liquid contained in the liquid bubble can be identified by collecting the generated gas by heat generation gas analysis and analyzing the gas composition.

The solubility parameter of the liquid contained in the liquid bubbles is preferably 17.0 (MPa) ^1/2 or less, and more preferably 16.5 (MPa) ^1/2 or less. Since a liquid having a solubility parameter of 17.0 (MPa) ^1/2 or less has low compatibility with the above-described polymer, the solubility of the polymer in the liquid and / or the solubility of the liquid in the polymer is low, and thus in the heat-sensitive layer. It can be easily present as a liquid bubble (in a polymer having film-forming ability).

In the present invention, the solubility parameter refers to the solubility parameter of Hildebrand, and refers to an amount δ defined by δ = (ΔH / V) ^1/2 where ΔH is the heat of molar evaporation of the liquid and V is the molar volume. The unit of the solubility parameter is (MPa) ^1/2 . (Cal · cm ⁻³ ) ^1/2 is often used as the unit of the solubility parameter, and δ (MPa) ^1/2 = 2.0455 × δ (cal · cm ⁻³ ) is used between both units. ) There is a ^1/2 relational expression. Specifically, the solubility parameter 17.0 (MPa) ^1/2 is 8.3 (cal · cm ⁻³ ) ^1/2 . Examples of the liquid having a solubility parameter of 17.0 (MPa) ^1/2 or less include, but are not limited to, aliphatic hydrocarbons, alicyclic hydrocarbons, and alkylene oxide dialkyl ethers. From the viewpoints of economy and safety, aliphatic saturated hydrocarbons are preferred.

  The solubility parameter of the liquid contained in the liquid bubble can also be confirmed from the literature value by analyzing the gas composition generated by the heat generation gas analysis and specifying the structure.

As a liquid having a boiling point in the range of 210 to 270 ° C. and a solubility parameter of 17.0 (MPa) ^1/2 or less, for example, a linear, branched or cyclic hydrocarbon having 12 to 18 carbon atoms, Diethylene glycol butyl methyl ether (boiling point: 212 ° C., solubility parameter: 16.0 (MPa) ^1/2 ), diethylene glycol dibutyl ether (boiling point: 256 ° C., solubility parameter: 15.8 (MPa) ^1/2 ), triethylene glycol Dimethyl ether (boiling point: 216 ° C., solubility parameter: 16.2 (MPa) ^1/2 ), triethylene glycol butyl methyl ether (boiling point: 261 ° C., solubility parameter: 16.2 (MPa) ^1/2 ), tripropylene glycol Dimethyl ether (boiling point: 215 ° C, solubility parameter 15.1 ^{(MPa) 1/2),} and the like alkylene glycol dialkyl ethers such as. Two or more of these may be included.

From the viewpoint of further improving the initial sensitivity and the sensitivity after lapse of time, it is preferable that at least one liquid bubble is present within the irradiation area of the laser beam scanned in the exposure step when producing the waterless lithographic printing plate. The irradiation area of the laser beam of a general exposure machine is about 100 μm ² (a square with a side of about 10 μm).
The number of liquid bubbles contained in the portion of the heat sensitive layer where the inclined region does not exist can be obtained by TEM observation. More specifically, a sample is prepared from a direct-drawing waterless lithographic printing plate precursor by a continuous (ultra-thin) section method, and a TEM observation of the thermosensitive layer is performed under conditions of an acceleration voltage of 100 kV and a direct magnification of 8000 times. Based on the three-dimensional information of the horizontal section, the total number of liquid bubbles (diameter: 0.01 μm or more) in the depth direction of the horizontal section 1 μm ² ((vertical) 1 μm × (horizontal) 1 μm) of the heat-sensitive layer in the portion where the inclined region does not exist The number of liquid bubbles can be obtained by counting.

The spatial distribution of the liquid bubbles in the heat-sensitive layer may be uniform or modulated in the depth direction. From the viewpoint of further improving the initial sensitivity and the sensitivity after aging, the heat-sensitive layer 0.5 μm ³ ((vertical) 1 μm × (horizontal) where there is no inclined region from the interface with the silicone rubber layer to a depth of 0.5 μm 1 μm × (depth from the interface with the silicone rubber layer) 0.5 μm), the number of liquid bubbles having a diameter of 0.01 μm or more is preferably 2 or more, and more preferably 20 or more.

  The diameter of the liquid bubble is preferably 0.01 μm or more, more preferably 0.05 μm or more, and more preferably 0.1 μm or more. On the other hand, 1 μm or less is preferable, 0.5 μm or less is more preferable, and 0.3 μm or less is more preferable. The liquid bubbles having a diameter in the above range are preferably contained in an amount of 50% by volume or more, more preferably 80% by volume or more, and still more preferably 90% by volume or more of the entire liquid bubbles. The average diameter of the liquid bubbles is preferably 0.1 to 1 μm, more preferably 0.1 to 0.3 μm, and further preferably 0.25 μm or less. If the size of the liquid bubble is within the above range, the initial sensitivity and the sensitivity after aging are further improved.

  In the present invention, the diameter of the liquid bubble refers to the equivalent volume sphere equivalent diameter when the liquid bubble is assumed to be a true sphere. Moreover, the average diameter of a liquid bubble refers to the number average value calculated from a plurality of liquid bubbles having the above-mentioned diameter. The average diameter of the liquid bubbles contained in the heat-sensitive layer in the portion where the inclined region does not exist can be obtained by TEM observation. More specifically, a sample is prepared from a direct-drawing waterless lithographic printing plate precursor by a continuous (ultra-thin) section method, and a TEM observation of the thermosensitive layer is performed under conditions of an acceleration voltage of 100 kV and a direct magnification of 8000 times. The average diameter can be obtained by measuring the diameter of 50 randomly selected liquid bubbles based on the three-dimensional information of the horizontal section and calculating the number average value thereof.

  The content of the liquid bubbles in the heat-sensitive layer is preferably 0.1% by volume or more, more preferably 1% by volume or more, and more preferably 5% by volume or more of the heat-sensitive layer where the inclined region does not exist. On the other hand, from the viewpoint of solvent resistance and printing durability, 50% by volume or less is preferable, 40% by volume or less is more preferable, and 20% by volume or less is more preferable.

  When the heat-sensitive layer has liquid bubbles, the heat softening point of the heat-sensitive layer is preferably 50 ° C. or higher, and more preferably 60 ° C. or higher. If the thermal softening point is 50 ° C. or higher, the flow of the heat-sensitive layer at room temperature can be suppressed, and thus the sensitivity after aging can be further improved. The heat softening point of the heat sensitive layer largely depends on the heat softening point of the polymer having active hydrogen which is the main component of the heat sensitive layer. For this reason, it is preferable to use a polymer having a thermal softening point of 50 ° C. or higher as the polymer having active hydrogen. Among them, a polymer having an alcoholic hydroxyl group, a phenolic hydroxyl group, and a carboxyl group having a thermal softening point of 50 ° C. or higher is more preferable, and a polymer having a phenolic hydroxyl group having a thermal softening point of 50 ° C. or higher (p-hydroxystyrene homopolymer). Or a copolymer, a novolak resin, a resole resin, etc.) are more preferable.

  In the direct-drawing waterless lithographic printing plate precursor of the present invention, the average film thickness of the heat-sensitive layer in the portion where no inclined region exists is preferably 0.3 μm or more, more preferably 0.8 μm or more. On the other hand, it is preferably 10 μm or less, and more preferably 7 μm or less. When the average film thickness of the heat-sensitive layer where there is no inclined region is 0.3 μm or more, the developability is hardly lowered, and when it is 10 μm or less, the effect of improving the blister resistance is easily manifested, and the economy It is not disadvantageous from a general point of view. Here, the average film thickness of the heat-sensitive layer in the portion where there is no inclined region can be obtained by TEM observation. More specifically, a sample is prepared from a direct-drawing waterless lithographic printing plate precursor by an ultrathin section method, and TEM observation is performed under conditions of an acceleration voltage of 100 kV and a direct magnification of 2000 times. In a TEM photograph of a vertical cross section, the average film thickness is obtained by measuring the film thickness at 10 locations randomly selected from the heat-sensitive layer in a smooth portion without an inclined region and calculating the number average value thereof. Can do.

  In the direct-drawing waterless planographic printing plate precursor of the present invention, as the silicone rubber layer, a layer obtained by applying an addition reaction type silicone rubber layer composition or a condensation reaction type silicone rubber layer composition, Examples include a layer obtained by applying a solution and (heating) drying.

  The addition reaction type silicone rubber layer composition preferably contains at least a vinyl group-containing organopolysiloxane, a SiH group-containing compound (addition reaction type crosslinking agent) and a curing catalyst. Furthermore, you may contain reaction inhibitor.

The vinyl group-containing organopolysiloxane has a structure represented by the following general formula (I) and has a vinyl group at the end of the main chain or in the main chain. Of these, those having a vinyl group at the end of the main chain are preferred. Two or more of these may be contained.
-(SiR ¹ R ² -O-) _n- (I)
In the formula, n represents an integer of 2 or more, and R ¹ and R ² may be the same or different and each represents a saturated or unsaturated hydrocarbon group having 1 to 50 carbon atoms. The hydrocarbon group may be linear, branched or cyclic and may contain an aromatic ring.

In the above formula, 50% or more of R ¹ and R ² are preferably methyl groups from the viewpoint of ink repellency of the printing plate. Further, from the viewpoints of handleability, ink repellency of the printing plate, and scratch resistance, the weight average molecular weight of the vinyl group-containing organopolysiloxane is preferably 10,000 to 600,000.

  Examples of the SiH group-containing compound include organohydrogenpolysiloxanes and organic polymers having a diorganohydrogensilyl group, and organohydrogenpolysiloxanes are preferred. Two or more of these may be contained.

Organohydrogenpolysiloxane has a linear, cyclic, branched, and network molecular structure, with both molecular chain terminal trimethylsiloxy group-capped polymethylhydrogensiloxane and molecular chain both terminal trimethylsiloxy group-capped dimethylsiloxane methyl. Hydrogen siloxane copolymer, trimethylsiloxy group-capped dimethylsiloxane / methylhydrogensiloxane / methylphenylsiloxane copolymer, molecular chain dimethylhydrogensiloxy group-capped dimethylpolysiloxane, molecular chain both-end dimethylhydro Jenshirokishi group dimethylsiloxane-methylphenylsiloxane copolymers, both molecular terminals with dimethylhydrogensiloxy groups at methylphenyl polysiloxane, formula siloxane represented by R ₃ SiO _1/2 Units and _formula siloxane units represented by the formula R 2 _{HSiO 1/2:} organopolysiloxane copolymers composed of siloxane units represented by _{SiO 4/2, wherein:} the siloxane units represented by R 2 _{HSiO 1/2} Organopolysiloxane copolymer comprising a siloxane unit represented by the formula: SiO _4/2 , a siloxane unit represented by the formula: RHSiO _2/2 and a siloxane unit represented by the formula: RSiO _3/2 or a formula: HSiO _3/2 And an organopolysiloxane copolymer comprising a siloxane unit represented by Two or more of these organopolysiloxanes may be used. In the above formula, R is a monovalent hydrocarbon group other than an alkenyl group, and may be substituted. For example, alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group; aryl groups such as phenyl group, tolyl group, xylyl group, naphthyl group; benzyl group, phenethyl group, etc. Aralkyl groups; halogenated alkyl groups such as chloromethyl group, 3-chloropropyl group and 3,3,3-trifluoropropyl group are exemplified.

  Examples of the organic polymer having a diorganohydrogensilyl group include dimethylhydrogensilyl group-containing (meth) acrylic monomers such as dimethylhydrogensilyl (meth) acrylate, dimethylhydrogensilylpropyl (meth) acrylate, and ( Methyl) methacrylate, ethyl (meth) acrylate, butyl (meth) acrylate, ethyl hexyl (meth) acrylate, lauryl (meth) acrylate, styrene, α-methylstyrene, maleic acid, vinyl acetate, allyl acetate, etc. And oligomers obtained by copolymerization with the above monomers.

  The content of the SiH group-containing compound is preferably 0.5% by weight or more, more preferably 1% by weight or more in the silicone rubber layer composition from the viewpoint of curability of the silicone rubber layer. Moreover, 20 weight% or less is preferable and 15 weight% or less is more preferable.

  Examples of the reaction inhibitor include nitrogen-containing compounds, phosphorus compounds and unsaturated alcohols, and acetylene group-containing alcohols are preferably used. Two or more of these may be contained. By containing these reaction inhibitors, the curing rate of the silicone rubber layer can be adjusted. The content of the reaction inhibitor is preferably 0.01% by weight or more, more preferably 0.1% by weight or more in the silicone rubber layer composition, from the viewpoint of the stability of the silicone rubber layer composition or its solution. Further, from the viewpoint of curability of the silicone rubber layer, the content is preferably 20% by weight or less, more preferably 15% by weight or less in the silicone rubber layer composition.

  The curing catalyst is selected from known ones. Preferred are platinum compounds, and specific examples include platinum alone, platinum chloride, chloroplatinic acid, olefin coordinated platinum, platinum alcohol-modified complexes, platinum methylvinylpolysiloxane complexes, and the like. Two or more of these may be contained. The content of the curing catalyst is preferably 0.001% by weight or more, more preferably 0.01% by weight or more in the silicone rubber layer composition from the viewpoint of curability of the silicone rubber layer. Further, from the viewpoint of the stability of the silicone rubber layer composition and the solution thereof, the content is preferably 20% by weight or less, more preferably 15% by weight or less in the silicone rubber layer composition.

  In addition to these components, hydroxyl group-containing organopolysiloxane, hydrolyzable functional group-containing silane (or siloxane), known fillers such as silica for the purpose of improving rubber strength, and known for the purpose of improving adhesiveness. The silane coupling agent may be contained. As the silane coupling agent, alkoxysilanes, acetoxysilanes, ketoximinosilanes and the like are preferable, and those having a vinyl group or an allyl group are particularly preferable.

  The condensation reaction type silicone rubber layer composition preferably contains at least a hydroxyl group-containing organopolysiloxane, a crosslinking agent and a curing catalyst.

  The hydroxyl group-containing organopolysiloxane has a structure represented by the general formula (I) and has a hydroxyl group at the end of the main chain or in the main chain. Of these, those having a hydroxyl group at the end of the main chain are preferred. Two or more of these may be contained.

Examples of the crosslinking agent include silicon compounds such as a deacetic acid type, a deoxime type, a dealcohol type, a deacetone type, a deamide type, and a dehydroxylamine type represented by the following general formula (II).
(R ³ ) _4-m SiX _m (II)
In the formula, m represents an integer of 2 to 4, R ³ may be the same or different, and represents a substituted or unsubstituted alkyl group, alkenyl group, aryl group having 1 or more carbon atoms, or a combination thereof. Show. X may be the same or different and represents a hydrolyzable group. Examples of hydrolyzable groups include acyloxy groups such as acetoxy group, ketoxime groups such as methylethylketoxime group, alkoxy groups such as methoxy group, ethoxy group, propoxy group, butoxy group, alkenyloxy groups such as isopropenoxy group, acetylethylamino group And an aminoxy group such as a dimethylaminoxy group. In the above formula, the number m of hydrolyzable groups is preferably 3 or 4.

  Specific compounds include methyltriacetoxysilane, ethyltriacetoxysilane, vinyltriacetoxysilane, allyltriacetoxysilane, phenyltriacetoxysilane, tetraacetoxysilane and other acetoxysilanes, vinylmethylbis (methylethylketoximino) silane , Methyl tris (methyl ethyl ketoximino) silane, ethyl tris (methyl ethyl ketoximino) silane, vinyl tris (methyl ethyl ketoximino) silane, allyl tris (methyl ethyl ketoximino) silane, phenyl tris (methyl ethyl ketoximino) silane, tetrakis (methyl ethyl ketoximino) silane, etc. Ketoximinosilanes, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethylto Alkoxysilanes such as ethoxysilane, tetraethoxysilane, tetrapropoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltriethoxysilane, vinyltriisopropoxysilane, vinyltrisisopropenoxysilane, diisopropenoxydimethylsilane Alkenyloxysilanes such as triisopropenoxymethylsilane, tetraallyloxysilane, and the like, but are not limited thereto. Among these, acetoxysilanes and ketoximinosilanes are preferable from the viewpoint of the curing speed of the silicone rubber layer, handling properties, and the like. Two or more of these may be contained.

  The content of the crosslinking agent is preferably 0.5% by weight or more and more preferably 1% by weight or more in the silicone rubber layer composition from the viewpoint of the stability of the silicone rubber layer composition and the solution thereof. Further, from the viewpoint of the strength of the silicone rubber layer and the scratch resistance of the printing plate, the content is preferably 20% by weight or less, more preferably 15% by weight or less in the silicone rubber layer composition.

  Examples of the curing catalyst include organic carboxylic acids, acids, alkalis, amines, metal alkoxides, metal diketenates, organic acid salts of metals such as tin, lead, zinc, iron, cobalt, calcium, and manganese. Specific examples include dibutyltin diacetate, dibutyltin dioctate, dibutyltin dilaurate, zinc octylate, and iron octylate. Two or more of these may be contained.

  The content of the curing catalyst is preferably 0.001% by weight or more, and more preferably 0.01% by weight or more in the silicone rubber layer composition from the viewpoints of curability and adhesiveness of the silicone rubber layer. Further, from the viewpoint of the stability of the silicone rubber layer composition and its solution, it is preferably 15% by weight or less, more preferably 10% by weight or less in the silicone rubber layer composition.

  In addition to these components, a known filler such as silica may be contained for the purpose of improving rubber strength.

  Further, for the purpose of imparting plate inspection properties to the waterless lithographic printing plate after development, it is preferable to contain a colored pigment in the silicone rubber layer. Here, in the present invention, the colored pigment refers to a pigment that absorbs any light in the visible light wavelength region (380 to 780 nm).

  In general, pigments are insoluble in solvents such as water and aliphatic hydrocarbons. Therefore, by including pigments, water and organic chemicals used in the development process can be used compared to the case of containing dyes that are soluble in water and solvents. Dye extraction with solvents and various cleaning agents in the ink used in the printing process is remarkably suppressed.

  Examples of the plate inspection property of the waterless planographic printing plate after development include visual plate inspection property by visual inspection and device plate inspection property by a halftone dot area ratio measuring device. In general, since the image inspection ability is lower than the visual inspection ability, the waterless lithographic printing plate having good inspection performance often has good visual inspection ability.

A general halftone dot area ratio measuring device has blue light (wavelength 400 to 500 nm), green light (wavelength 500 to 600 nm), red light (wavelength 600 to 700 nm), on a halftone dot portion formed on a printing plate. Alternatively, white light (wavelength of 400 to 700 nm) is irradiated, and the halftone dot area ratio is calculated from the difference in the amount of reflected light between the image area / non-image area. For this reason, when the difference in the amount of reflected light between the image area and the non-image area is small, or when there is no difference in the amount of reflected light, it is difficult to measure the dot area ratio, and the device inspection performance is degraded. Many of the organic compounds that make up the heat-insulating and heat-sensitive layers of direct-drawing waterless lithographic printing plate precursors absorb blue light, so use a silicone rubber layer colored with colored pigments such as yellow and orange that absorb blue light. In this case, the difference in the amount of reflected light between the image area / non-image area is reduced, and the device inspection is deteriorated. Furthermore, the visual plate inspection property may also deteriorate. For these reasons, it is preferable to use a colored pigment that absorbs green light or red light from the viewpoints of instrument inspection and visual inspection. Furthermore, among colored pigments that absorb green light or red light, colored pigments having a density of 3 g / cm ³ or less are preferable from the viewpoint of dispersibility in the silicone rubber layer composition and its solution. Among colored pigments that absorb green light or red light, those having a density of 3 g / cm ³ or less include cobalt blue, bitumen, hydrous oxalate, ultramarine, carbon black, extender pigments (lime carbonate powder, precipitated) Printing pigments in which basic calcium carbonate, gypsum, asbestos, clay, silica powder, diatomaceous earth, talc, basic magnesium carbonate, alumina white) are dyed with dyes such as rhodamine, methyl violet, peacock blue, alkali blue, malachite green, alizarin , Alkali blue, aniline black, resol red, lake red C, brilliant carmine 6B, watch young red, Bordeaux 10B, para red, lake red 4R, naphthol red, chromophthalscarlet RN, phthalocyanine blue, fast sky blue, Examples include phthalocyanine green, anthraquinone pigment, perylene red, thioindigo red, indanthrone blue, quinacridone red, quinacridone violet, dioxazine violet, and naphthol green B. Two or more of these may be contained.

  In the direct-drawing waterless planographic printing plate precursor of the present invention, the content of the colored pigment is preferably 0.1% by volume or more, more preferably 0.2% by volume or more in the silicone rubber layer. Moreover, from a viewpoint of maintaining the ink repellency of a silicone rubber layer, 20 volume% or less is preferable and 10 volume% or less is more preferable.

  In order to improve the dispersibility of the colored pigment in the silicone rubber layer, the silicone rubber layer composition preferably contains a pigment dispersant. By containing the pigment dispersant, it is possible to suppress the aggregation of the colored pigment that occurs with time in the silicone rubber layer composition or its solution when the silicone rubber layer composition is diluted with a solvent. As the pigment dispersant, a pigment dispersant that wets the pigment surface well and has good affinity with low-polar compounds such as organopolysiloxane and a solvent used for diluting the colored pigment-containing silicone liquid described later is preferable. If it is such a pigment dispersant, a well-known pigment dispersant can be used. The pigment dispersant is sometimes used as a name such as a surfactant or a surface modifier. Examples of the pigment dispersant include an organic complex compound composed of a metal and an organic compound, an amine pigment dispersant, an acid pigment dispersant, and a nonionic surfactant. Among these, an organic complex compound composed of a metal and an organic compound or an amine pigment dispersant is preferable.

  Examples of the metal and organic compound that form the organic complex compound include the metal and organic compound that form the metal complex compound exemplified above as the crosslinking agent of the heat-sensitive layer. Among these, as the organic compound, acid compounds such as carboxylic acid, phosphoric acid, and sulfonic acid, and diketones, ketoesters, and diester compounds capable of forming a chelate ring with a metal are preferable from the viewpoint of coordination power with the metal.

  The simplest organic complex compound used as a pigment dispersant can be obtained by stirring the organic compound and metal alkoxide at room temperature or under heating and exchanging the ligand. It is preferable to coordinate one or more molecules of the organic compound to one metal.

  An example of a commercially available organic complex compound composed of a metal and an organic compound is given below. Aluminum type: “Octope” (registered trademark) Al, “Olyp” AOO, AOS (above, manufactured by Hope Pharmaceutical Co., Ltd.), “Plenact” (registered trademark) AL-M (produced by Ajinomoto Fine Techno Co., Ltd.), and the like. Titanium-based: “Pureact” KR-TTS, KR46B, KR55, KR41B, KR38S, KR138S, KR238S, KR338X, KR9SA (above, manufactured by Ajinomoto Fine Techno Co., Ltd.), “KEN-REACT” (registered trademark) TTS-B, 5, 6, 7, 10, 11, 12, 15, 26S, 37BS, 43, 58CS, 62S, 36B, 46B, 101, 106, 110S, 112S, 126S, 137BS, 158DS, 201, 206, 212, 226, 237, 262S (above, manufactured by KENRICH).

  The organic complex compound can be suitably used particularly for an addition reaction type silicone rubber layer. In particular, organic complex compounds that do not contain primary or secondary amines, phosphorus, or sulfur in the molecule do not act as catalyst poisons for platinum catalysts. Therefore, when used for addition reaction type silicones that promote curing using platinum catalysts. It is very suitable for.

  On the other hand, as the amine pigment dispersant, there are a monoamine type having one amino group in the molecule and a polyamine type having a plurality of amino groups in the molecule, both of which can be suitably used. Specific examples include “Solsperse” (registered trademark) 9000, 13240, 13650, 13940, 17000, 18000, 19000, 28000 (above, manufactured by LUBRIZOL).

The pigment dispersant is preferably contained in an amount of ² to 30 mg / m ^{2 with} respect to the surface area of the pigment. In other words, for example, when 10 g of a pigment having a specific surface area of 50 m ² / g is contained, the content of the pigment dispersant is preferably 1 to 15 g.

In the direct-drawing waterless lithographic printing plate precursor according to the present invention, the average film thickness of the silicone rubber layer on the heat-sensitive layer in a portion where there is no inclined region is preferably 0.5 to 20 μm. By setting the average film thickness of the silicone rubber layer on the heat-sensitive layer where the inclined region does not exist to 0.5 g / m ² or more, the ink repellency, scratch resistance and printing durability of the printing plate become sufficient, and 20 g / m ^By setting it to ² or less, it is not disadvantageous from an economical point of view, and developability and ink mileage are hardly lowered. Here, the average film thickness of the silicone rubber layer on the heat-sensitive layer in the portion where the inclined region does not exist can be determined by TEM observation. More specifically, a sample is prepared from a direct-drawing waterless lithographic printing plate precursor by an ultrathin section method, and TEM observation is performed under conditions of an acceleration voltage of 100 kV and a direct magnification of 2000 times. In a TEM photograph of a vertical cross section, the film thickness was measured at 10 locations randomly selected from the silicone rubber layer on the heat-sensitive layer in a smooth portion without an inclined region, and the average value was calculated by calculating the number average value thereof. The film thickness can be determined.

  For the purpose of improving adhesion between the substrate and the heat-sensitive layer, preventing light halation, improving plate inspection, improving heat insulation, and improving printing durability, a heat insulating layer may be provided on the substrate. As a heat insulation layer used for this invention, the heat insulation layer described in Unexamined-Japanese-Patent No. 2004-199016, Unexamined-Japanese-Patent No. 2004-334025, Unexamined-Japanese-Patent No. 2006-276385 etc. can be mentioned, for example.

  The direct-drawing waterless planographic printing plate precursor of the present invention may have a protective film and / or a slip sheet for the purpose of protecting the silicone rubber layer.

  As the protective film, a film having a thickness of 100 μm or less that transmits light of an exposure light source wavelength favorably is preferable. Typical examples include polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, cellophane, and the like. In addition, for the purpose of preventing exposure of the original plate due to exposure, various protective materials such as various light absorbers, photobleachable substances, and photochromic substances described in JP-A-2-063050 may be provided. Good.

The slip sheet is preferably one weighing 30 to 120 g / ^{m 2,} more preferably from 30~90g / ^{m 2.} If the weight is 30 g / m ² or more, the mechanical strength is sufficient, and if it is 120 g / m ² or less, not only is it economically advantageous, but a laminate of a direct-drawing waterless lithographic printing plate precursor and paper is used. Thinning and workability are advantageous. Examples of interleaving paper preferably used include, for example, information recording base paper 40 g / m ² (manufactured by Nagoya Pulp Co., Ltd.), metal interleaving paper 30 g / m ² (manufactured by Nagoya Pulp Co., Ltd.), unbleached kraft paper 50 g / m. ² (manufactured by Chuetsu Pulp Co., Ltd.), NIP paper 52 g / m ² (manufactured by Chuetsu Pulp Co., Ltd.), pure white roll paper 45 g / m ² (manufactured by Oji Paper Co., Ltd.), Kurpack 73 g / m ² (Oji But not limited to these.
Next, a method for producing the direct-drawing waterless planographic printing plate precursor of the present invention will be described. The method for producing a direct-drawing waterless lithographic printing plate precursor according to the present invention includes at least a step of forming a heat-sensitive layer and a step of forming a silicone rubber layer on a substrate. Furthermore, another process may be provided. For example, in the step of forming a heat sensitive layer, (a) a heat sensitive layer composition or a heat sensitive layer composition solution is applied on a substrate which may have a heat insulating layer, and dried if necessary to form a heat sensitive layer. It is good also as a process. Further, the step of forming the silicone rubber layer may be a step of forming the silicone rubber layer by applying a silicone rubber layer composition or a silicone rubber layer composition solution on the heat-sensitive layer (b) and drying as necessary. Good.

  (A) The process of forming a heat sensitive layer by apply | coating a heat sensitive layer composition or a heat sensitive layer composition solution on the board | substrate which may have a heat insulation layer, and drying as needed is demonstrated.

  When the heat-sensitive layer composition is applied to form a heat-sensitive layer, the heat-sensitive layer composition is a solvent-free liquid composed of the material forming the heat-sensitive layer, and the above-mentioned heat-sensitive layer components and other components as necessary Can be prepared by mixing.

The heat-sensitive layer composition solution has a solubility parameter of 17.0 (MPa) ^½ or less, a solvent containing a liquid having a boiling point in the range of 210 to 270 ° C., and a solubility parameter of 17.0 (MPa). It is preferable to contain a solvent exceeding ^1/2 , and a liquid bubble containing a liquid having a boiling point in the range of 210 to 270 ° C. can be formed in the heat-sensitive layer.

Specific examples of the solvent having a solubility parameter of 17.0 (MPa) ^1/2 or less and having a boiling point in the range of 210 to 270 ° C. include straight chain, branched or 12 to 18 carbon atoms. Cyclic hydrocarbon, normal paraffin grade M (boiling point: 219 to 247 ° C., solubility parameter: 16.2 (MPa) ^1/2 (manufactured by Nippon Oil Corporation)), normal paraffin grade H (boiling point: 244 to 262) ° C, solubility parameter: 16.2 (MPa) ^1/2 (manufactured by Nippon Oil Corporation)), “NS Clean” 230 (boiling point: 227 ° C., solubility parameter: 16.2 (MPa) ^1/2 (( Co., Ltd.) JOMO San Energy)), "Isopar" (registered trademark) M (boiling point: 223~254 ℃, solubility parameter: 14.7 ^{(MPa) 1/2} (Esso chemical (Co. Ltd.)), "IP Solvent" 2028 (boiling point: 213~262 ℃, solubility parameter: 14.3 ^{(MPa) 1/2} (Idemitsu Kosan Co., Ltd.)), "IP clean" HX (boiling point: 222-261 ° C, solubility parameter: 14.3 (MPa) ^1/2 (made by Idemitsu Kosan Co., Ltd.)) and other saturated aliphatic hydrocarbons, “Naphthezol” (registered trademark) 220 (boiling point: 221 to 240 ° C., solubility parameter: 16.4 (MPa) ^1/2 (manufactured by Nippon Oil Corporation)) and the like, diethylene glycol butyl methyl ether (boiling point: 212 ° C., solubility parameter: 16.0 (MPa) ^1/2 ) , diethylene glycol dibutyl ether (boiling point: 256 ° C., solubility parameter: 15.8 ^{(MPa) 1/2),} triethylene glycol dimethyl Agent Le (boiling point: 216 ° C., solubility parameter: 16.2 ^{(MPa) 1/2),} triethylene glycol butyl methyl ether (boiling point: 261 ° C., solubility parameter: 16.2 ^{(MPa) 1/2),} tripropylene glycol Examples include alkylene glycol dialkyl ethers such as dimethyl ether (boiling point: 215 ° C., solubility parameter: 15.1 (MPa) ^1/2 ). Two or more of these may be included.

Further, as a solvent containing a liquid having a solubility parameter of 17.0 (MPa) ^1/2 or less and having a boiling point in the range of 210 to 270 ° C., specifically, “naphthethol” 200 (boiling point: 201 ˜217 ° C., solubility parameter: 16.2 (MPa) ^1/2 (manufactured by Nippon Oil Corporation), “Dust Clean” 300 (boiling point: 201-217 ° C., solubility parameter: 16.2 (MPa) ^{1 / 2} (Matsumura Oil Co., Ltd.)), “Dust Clean” 300AF (boiling point: 201-217 ° C., solubility parameter: 16.2 (MPa) ^1/2 (Matsumura Oil Co., Ltd.)), polyethylene glycol dimethyl ether (Boiling point: 264 to 294 ° C., solubility parameter: 16.6 (MPa) ^1/2 ) and the like. Two or more of these may be included.

The ratio of the liquid having a boiling point in the range of 210 to 270 ° C. in the solvent having a solubility parameter of 17.0 (MPa) ^1/2 or less contained in the heat-sensitive layer composition solution is preferably 80% by weight or more, and 90% by weight or more. Is more preferable, 95% by weight or more is more preferable, and 100% by weight is further preferable.

The content of the solvent having a solubility parameter of 17.0 (MPa) ^1/2 or less and having a boiling point in the range of 210 to 270 ° C. is solid from the viewpoint of further improving the initial sensitivity and the sensitivity after aging. 0.1 parts by weight or more is preferable with respect to 100 parts by weight per minute, and 1 part by weight or more is more preferable. On the other hand, from the viewpoint of applicability of the heat-sensitive layer composition solution, 60 parts by weight or less is preferable with respect to 100 parts by weight of the heat-sensitive layer solid content, and 25 parts by weight or less is more preferable. Further, from the viewpoint of further improving the initial sensitivity and sensitivity after aging, the content in the heat-sensitive layer composition solution is preferably 0.1% by weight or more, and more preferably 0.5% by weight or more. On the other hand, from the viewpoint of applicability of the heat-sensitive layer composition solution, it is preferably 10% by weight or less, more preferably 7% by weight or less, and more preferably 5% by weight or less in the heat-sensitive layer composition solution.

As the solvent having a solubility parameter exceeding 17.0 (MPa) ^1/2 , those capable of dissolving or dispersing the heat-sensitive layer constituents are preferable. For example, alcohols, ethers, ketones, esters, amides and the like can be mentioned. Two or more of these may be contained.

  Examples of alcohols include methanol, ethanol, 1-propanol, isopropanol, 1-butanol, isobutanol, 2-butanol, 2-methyl-2-propanol, 1-pentanol, 2-methyl-1-butanol, 3 -Methyl-1-butanol, 2-pentanol, 3-pentanol, 2-methyl-2-butanol, 1-hexanol, 2-hexanol, 3-hexanol, 4-methyl-2-pentanol, 2-ethylbutanol 1-heptanol, 2-heptanol, 3-heptanol, 2,4-dimethylpent-3-ol, 1-octanol, 2-octanol, 2-ethylhexanol, 1-nonanol, 2,6-dimethyl-4-heptanol , 1-decanol, ethylene glycol, diethylene glycol , Triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, 1,4-butylene glycol, 2,3-butylene glycol, 2-ethyl-1,3-hexanediol, glycerin, benzyl alcohol, α-methyl Examples include benzyl alcohol, cyclopentanol, cyclohexanol, methylcyclohexanol, furfuryl alcohol, and tetrahydrofurfuryl alcohol.

  Examples of ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl hexyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, ethylene glycol dimethyl ether. , Ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol Cole diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, Propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether Ter, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether, dipropylene glycol dibutyl ether, tripropylene glycol monomethyl ether, methyl phenyl ether, dimethoxymethane, diether acetal, propylene oxide, dioxane, dimethyl dioxane , Trioxane, dioxolane, methyldioxolane, tetrahydrofuran, tetrahydropyran and the like.

  Examples of ketones include acetone, methyl ethyl ketone, methyl propyl ketone, diethyl ketone, methyl butyl ketone, methyl isobutyl ketone, ethyl propyl ketone, ethyl butyl ketone, dipropyl ketone, dibutyl ketone, diisobutyl ketone, methyl pentyl ketone, methyl hexyl. Ketone, ethyl pentyl ketone, propyl butyl ketone, ethyl hexyl ketone, propyl pentyl ketone, propyl hexyl ketone, butyl pentyl ketone, butyl hexyl ketone, dipentyl ketone, pentyl hexyl ketone, dihexyl ketone, methyl isobutenyl ketone, diacetone alcohol, cyclohexane Pentanone, cyclohexanone, methylcyclohexanone, methyl phenyl ketone, isophorone, acetylacetone, acetonyl Acetone and the like.

  Examples of esters include methyl formate, ethyl formate, butyl formate, pentyl formate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, hexyl acetate, cyclohexyl acetate, phenyl acetate, propion Methyl acetate, ethyl propionate, propyl propionate, butyl propionate, pentyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, pentyl butyrate, ethyl crotonate, butyl crotonate, methyl benzoate, ethyl benzoate, benzyl benzoate , Methyl lactate, ethyl lactate, propyl lactate, butyl lactate, pentyl lactate, hexyl lactate, cyclohexyl lactate, methyl salicylate, ethyl salicylate, ethylene glycol monomethyl ether acetate, ethylene glycol Ethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triethylene glycol monomethyl ether acetate, methoxybutyl acetate, dimethyl oxalate, diethyl oxalate, dimethyl malonate, diethyl malonate, dimethyl maleate Diethyl maleate, γ-butyrolactone, γ-valerolactone, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate and the like.

  Examples of amides include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and the like.

  In addition, methyl carbamate, ethyl carbamate, tetramethyl urea, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, sulfolane, acetonitrile and the like may be contained.

Among the above solvents, a solvent having a solubility parameter of 17.0 (MPa) ^1/2 or less and compatible with a liquid having a boiling point in the range of 210 to 270 ° C. is particularly preferable.
The size of the liquid bubbles is closely related to the boiling point of the solvent having a solubility parameter exceeding 17.0 (MPa) ^1/2 and the ambient temperature when the heat-sensitive layer composition solution is applied. As a solvent having a solubility parameter exceeding 17.0 (MPa) ^1/2 , when a low-boiling solvent that easily evaporates at the ambient temperature when applying the heat-sensitive layer composition solution is used, the low-boiling solvent is quickly used. In order to evaporate and dry before the adjacent liquid bubble forming components gather, small liquid bubbles are formed in the heat sensitive layer. On the other hand, when a high-boiling solvent that does not easily evaporate at the ambient temperature when applying the heat-sensitive layer composition solution is used, the high-boiling solvent evaporates slowly and dries while the adjacent liquid bubble forming components gather. Large liquid bubbles are formed in the heat-sensitive layer.

In the solvent having the solubility parameter exceeding 17.0 (MPa) ^1/2 , the solvent having a boiling point of 30 to 200 ° C. is preferably 80% by weight or more, and more preferably 95% by weight or more. Moreover, it is more preferable to contain 80 weight% or more of solvent with a boiling point of 80 degrees C or less, and it is more preferable to contain 95 weight% or more. Moreover, it is more preferable to contain 80 weight% or more of solvent with a boiling point of 70 degrees C or less, and it is more preferable to contain 95 weight% or more. By containing 80% by weight or more of a solvent having a boiling point of 30 ° C. or higher, a stable coating solution can be easily prepared at room temperature without using a special cooling device. Further, by containing 80% by weight or more of a solvent having a boiling point of 200 ° C. or less, it can be easily removed from the heat-sensitive layer by drying described later.

Further, when the boiling point of the solvent having a solubility parameter exceeding 17.0 (MPa) ^1/2 is lower than the thermal softening point of the polymer having active hydrogen, it is advantageous for the formation of liquid bubbles.

The heat-sensitive layer composition solution has a heat-sensitive layer constituent component and a solubility parameter of 17.0 (MPa) ^1/2 or less, a solvent having a boiling point in the range of 210 to 270 ° C., and a solubility parameter of 17.0. (MPa) ^Contains more than ^1/2 solvent and other components as required. The concentration of the total solid content in the heat-sensitive layer composition solution is preferably 2 to 50% by weight.

  The heat-sensitive layer composition or the heat-sensitive layer composition solution may be applied directly on the substrate, or if necessary, the heat-sensitive layer composition solution may be applied on a substrate having a resin layer such as a heat insulating layer. It is preferable to degrease the coated surface of the substrate.

  Examples of coating devices include slit die coaters, direct gravure coaters, offset gravure coaters, reverse roll coaters, natural roll coaters, air knife coaters, roll blade coaters, variver roll blade coaters, two stream coaters, rod coaters, and dip coaters. , Curtain coater, spin coater and the like. A slit die coater, a gravure coater, and a roll coater are particularly preferable in terms of coating film accuracy, productivity, and cost.

The coating weight of the heat-sensitive layer composition solution is suitably in the range of 0.1 to 10 g / m ² in terms of weight after drying in terms of printing durability of the printing plate and diluting solvent being easy to evaporate and excellent productivity. Is in the range of 0.5-7 g / m ² . Drying of the heat-sensitive layer composition solution is performed without heating or under heating. In the case of heating, it is preferable to dry at a temperature of 30 to 190 ° C., more preferably 50 to 150 ° C. for 30 seconds to 5 minutes using a hot air dryer or an infrared dryer.

Next, (b) a step of forming a silicone rubber layer by applying a silicone rubber layer composition or a silicone rubber layer composition solution on the heat-sensitive layer and drying it as necessary will be described. Here, the silicone rubber layer composition is a solvent-free liquid composed of a material forming the silicone rubber layer, and is a diluent containing the silicone rubber layer composition and a solvent.
Examples of the solvent used in the dispersion of the colored pigment and the silicone rubber layer composition solution include aliphatic saturated hydrocarbons, aliphatic unsaturated hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, ethers, and the like. It is done. The solubility parameter of these solvents is preferably 17.0 (MPa) ^1/2 or less, and more preferably 15.5 (MPa) ^1/2 or less. For example, hexane, heptane, octane, nonane, decane, undecane, dodecane, isooctane, “Isopar (registered trademark)” C, “Isopar” E, “Isopar” G, “Isopar” H, “Isopar” K, “Isopar” Aliphatic saturated hydrocarbons such as L and “Isopar” M (manufactured by Exxon Chemical Co., Ltd.), aliphatic unsaturated hydrocarbons such as hexene, heptene, octene, nonene and decene, and fats such as cyclopentane, cyclohexane and methylcyclohexane Examples include cyclic hydrocarbons, halogenated hydrocarbons such as trifluorotrichloroethane, and ethers such as diethyl ether, diisopropyl ether, and diisobutyl ether. Two or more of these may be used. From the viewpoints of economy and safety, aliphatic and alicyclic hydrocarbons are preferred. These aliphatic and alicyclic hydrocarbons preferably have 4 to 20 carbon atoms, and more preferably 6 to 15 carbon atoms.

  Below, the specific preparation method of (i) silicone rubber layer composition and (ii) silicone rubber layer composition solution is described.

(I) Silicone rubber layer composition (solvent-free)
For example, a silicone paste is obtained by uniformly dispersing and mixing a hydroxyl or vinyl group-containing organopolysiloxane and, if necessary, a colored pigment, a pigment dispersant, and fine particles with a disperser. Examples of the disperser include three rolls, a ball mill, a bead mill, a sand mill, a disperser, a homogenizer, an attritor, and an ultrasonic disperser. In the resulting silicone paste, add a cross-linking agent, reaction catalyst, and other additives (reaction inhibitor, etc.) as necessary. Stir to homogenize the components and remove air bubbles mixed in the liquid. By removing, a silicone rubber layer composition is obtained. The defoaming may be natural defoaming or vacuum defoaming, but vacuum defoaming is more preferable.

(Ii) Silicone rubber layer composition solution (containing solvent)
For example, a silicone paste is obtained by uniformly dispersing and mixing a hydroxyl group or vinyl group-containing organopolysiloxane and, if necessary, a colored pigment, a pigment dispersant, and fine particles with the above-described disperser, and this is diluted with a solvent while stirring. . It is preferable to filter this using a general filter such as paper, plastic, or glass to remove impurities (such as giant particles of colored pigment that are not sufficiently dispersed) in the diluent. It is preferable to remove the water in the system by bubbling with dry air, dry nitrogen or the like from the diluted solution after filtration. Add the cross-linking agent, reaction catalyst, and other additives (such as reaction inhibitors) as necessary to the diluted liquid after sufficient water removal, and stir it to make the components uniform. Remove foam. Defoaming may be natural defoaming or vacuum defoaming.

Further, as another method for producing a silicone rubber layer composition solution containing a colored pigment, there is a method in which a colored pigment dispersion and a silicone liquid or a silicone dilution liquid are separately prepared in advance, and then both liquids are mixed. Can be mentioned. The colored pigment dispersion is obtained by adding a colored pigment and, if necessary, fine particles to a solution containing at least a pigment dispersant and a solvent, and uniformly dispersing and mixing them with the above-described disperser. On the other hand, the silicone liquid is obtained by mixing a hydroxyl group or vinyl group-containing organopolysiloxane, a crosslinking agent, a reaction catalyst, and other additives (such as a reaction inhibitor) as necessary. Moreover, a silicone dilution liquid can be obtained by diluting the obtained silicone liquid with a solvent.
When applying the silicone rubber layer composition or the silicone rubber layer composition solution, it is preferable from the viewpoint of adhesiveness to remove moisture adhering to the surface of the heat sensitive layer as much as possible. Specifically, a method in which the silicone rubber layer composition or the silicone rubber layer composition solution is applied in a space in which moisture is removed by filling or continuously supplying a dry gas can be mentioned. As the coating device, the same device as that for coating the heat-sensitive layer can be used.

  When the silicone rubber layer composition solution is applied, the silicone rubber layer composition solution is then dried to form a silicone rubber layer. You may heat-process for drying and hardening. The silicone rubber layer composition and the silicone rubber layer composition solution are preferably heated immediately after application from the viewpoint of curability and heat-sensitive layer adhesion.

  On the obtained direct-drawing waterless lithographic printing plate precursor, it is preferable to provide a protective film and / or slip paper for storage from the viewpoint of plate surface protection.

  In one aspect of the method for producing a direct-drawing waterless lithographic printing plate precursor according to the present invention, the step of forming the heat-sensitive layer is (1) heat-sensitive in the presence of a solid in the heat-sensitive layer composition solution for forming the heat-sensitive layer. Drying the layer composition solution. In another aspect, the step of forming the heat-sensitive layer includes (2) a step of applying a heat-sensitive layer composition or a heat-sensitive layer composition solution onto a substrate having an inclined region on the surface. Another aspect includes (3) a step of deforming or removing a part of the heat-sensitive layer. You may combine these processes. By including these steps, an inclined region can be easily formed on the surface of the heat-sensitive layer facing the silicone rubber layer.

  (1) The process of drying a heat sensitive layer composition solution in presence of a solid substance in the heat sensitive layer composition solution which forms a heat sensitive layer is demonstrated. Due to the space occupied by the solid matter, the heat-sensitive layer partially bulges and / or sinks to form an inclined region.

  The solid that is present in the heat-sensitive layer composition solution is a material that has low solubility in the heat-sensitive layer composition solution, and is a material that has low solubility to the extent that the solid can be retained throughout the process of forming the heat-sensitive layer. preferable. The material of the solid material may be either an inorganic material or an organic material, and an organic material is preferable from the viewpoint of dispersibility in the heat-sensitive layer composition solution. Examples of the inorganic material include silica, titania, and alumina. Examples of the organic material include an acrylic resin, a styrene resin, a silicone resin, and a copolymer thereof. In general, inorganic materials are hardly dissolved in organic solutions, but uncrosslinked organic materials may be dissolved in organic solutions. For this reason, when using an organic material, it is preferable to use organic particles having a crosslinked structure. The organic particles are preferably non-photosensitive particles. Here, the non-photosensitive particle means that at least light in a wavelength region of 700 to 1500 nm used for exposure, preferably light in a wavelength region of 750 to 1100 nm, is not absorbed at all or hardly (in terms of light absorption of particles). This refers to particles that do not undergo chemical reactions or physical changes such as combustion, melting, decomposition, vaporization, and explosion of the heat-sensitive layer components other than the particles themselves and particles), and light in a generally known wavelength range of 700 to 1500 nm. It is clearly different from photothermal conversion particles (carbon black and other pigments having photothermal conversion ability) that absorbs water and converts it into heat.

  Examples of the shape of the solid material include a spherical shape, a hemispherical shape, a lens shape, a polyhedron, and a columnar body, and a spherical shape is preferable from the viewpoint of uniformity. Examples of the spherical solid material include dense particles, hollow particles, porous particles, and core-shell particles. Solid particles are preferable from the viewpoints of economy and handleability. The shape of the solid in the heat-sensitive layer composition solution can be confirmed by observing the heat-sensitive layer composition solution before coating with an optical microscope (magnification: 3000 times).

  The preferred size of the solid varies depending on the average thickness of the heat-sensitive layer, but when the average thickness of the heat-sensitive layer is 0.1 to 10 μm, the average particle size of the solid is preferably 0.5 to 3.0 μm. . When the average particle size of the solid is 0.5 μm or more, a suitable inclined region is easily formed. In addition, from the relationship between the average particle size of the solid and the average thickness of the heat-sensitive layer, the average particle size of the solid is preferably 1/2 times or more of the average thickness of the heat-sensitive layer, more preferably 3/4 or more. Even more than double is even more preferable. If the average particle size of the solid is ½ times or more the average thickness of the heat-sensitive layer, the area of the inclined region and the fluctuation range of the shape are reduced, and a suitable inclined region is easily formed. Here, the average particle diameter of the solid material refers to a number average value obtained by calculating an equivalent volume sphere equivalent diameter assuming that the solid material is a true sphere from a plurality of particles. The average particle size of the solid contained in the heat sensitive layer can be determined by TEM observation. More specifically, a sample is prepared from a direct-drawing waterless lithographic printing plate precursor by a continuous (ultra-thin) section method, and a TEM observation of the thermosensitive layer is performed under the conditions of an acceleration voltage of 100 kV, a direct magnification of 2000 times, and a photo magnification of 13,000 to 17000 times. I do. Based on the three-dimensional information of the horizontal cross section, the average particle size can be obtained by measuring the particle size of 50 randomly selected solids and calculating the number average value thereof.

  For example, (i) a method of applying a heat-sensitive layer composition solution containing a solid, and drying the heat-sensitive layer composition solution in the presence of a solid; or (ii) applying a heat-sensitive layer composition solution after applying the solution. A method in which a solid material is charged into the film and the heat-sensitive layer composition solution is dried in the presence of the solid material is preferable. In the method (ii), the solid material is charged by, for example, a method in which a dispersion obtained by dispersing the solid material in a solvent that dissolves or swells the heat-sensitive layer is applied using a bar coater, or a spraying machine (spray gun). ) And spraying the surface. Among these, from the viewpoint of productivity and convenience, (i) a method of applying a heat-sensitive layer composition solution containing a solid and drying the heat-sensitive layer composition solution in the presence of the solid is more preferable. Drying of the heat-sensitive layer composition solution is performed without heating or under heating. In the case of heating, examples of the heating means include a hot air dryer and an infrared dryer. The heating temperature is preferably 30 ° C. or higher, and more preferably 50 ° C. or higher. On the other hand, 190 ° C. or lower is preferable, and 150 ° C. or lower is more preferable. The drying time is preferably 30 seconds to 5 minutes.

  (2) The process of applying the heat-sensitive layer composition or the heat-sensitive layer composition solution on the substrate having an inclined region on the surface will be described. Due to the space occupied by the inclined region, the heat-sensitive layer partially rises and / or sinks to form the inclined region. Here, the substrate may have a resin layer such as a heat insulating layer. As a method for forming the inclined region on the surface of the substrate, for example, a method of applying a dispersion liquid in which the solid material exemplified in (ii) of (1) above is dispersed using a bar coater, or a spraying machine. Examples thereof include a method of spraying the surface using a (spray gun), a method of cutting the substrate surface with a metal / diamond bit, and a method of embossing the substrate surface. When the substrate has a resin layer such as a heat-insulating layer, a method in which a patterned mold heated to a temperature higher than the thermal softening point of the resin layer is press-transferred onto the substrate surface (thermal imprint method), and a resin layer composition solution is applied. After that, the inclined region can also be formed by a method of drying the coating film in a state where the patterned mold is pressed against the surface of the coating film. Among these, from the viewpoint of productivity and convenience, a method of applying a dispersion liquid in which the solid material exemplified in (ii) above (1) is dispersed on a substrate using a bar coater, or a sprayer (spray) A method of spraying on the surface using a gun) is preferable. Furthermore, when the substrate has a resin layer such as a heat insulating layer, the solid dispersion medium preferably dissolves or swells the resin layer. By drying the dispersion, solids can be fixed to the resin layer, and dropping off of the solids during application of the heat-sensitive layer composition or the heat-sensitive layer composition solution can be suppressed. When applying the heat sensitive layer composition solution, it is preferably dried under the same conditions as in (1) above.

  (3) A process for deforming or removing a part of the heat-sensitive layer will be described. Examples of a method for deforming a part of the heat-sensitive layer include, for example, a method of drying a coating film while applying a patterned mold to the surface of the coating film after application of the heat-sensitive layer composition solution, and heat softening of the heat-sensitive layer. Examples thereof include a method (thermal imprint method) of press-transferring a patterned mold heated to a point or more to the surface of the heat-sensitive layer. Examples of the mold pattern include, but are not limited to, dots, holes, pillars, lines & spaces, checks, and lattice shapes. As a method for removing a part of the heat-sensitive layer, a method of cutting the surface of the heat-sensitive layer with a metal / diamond bite, a method of mechanically cutting a metal roller having irregularities on the surface against the surface of the heat-sensitive layer, Examples include a method of cutting by spraying a projecting material (shot blast method), a method of cutting a heat-sensitive layer with a laser such as a carbon dioxide laser, an Nd: YAG laser, or a semiconductor laser. Among these, from the viewpoint of uniformity and convenience, a method of drying the coating film after applying the heat-sensitive layer composition solution and pressing a patterned mold on the surface of the coating film is preferable. When applying the heat sensitive layer composition solution, it is preferably dried under the same conditions as in (1) above.

  Next, an example of a method for producing a waterless lithographic printing plate from the direct-drawing waterless lithographic printing plate precursor of the present invention will be described. Here, the waterless lithographic printing plate has an image receiving portion as an ink receiving layer, a non-image portion as an ink repellent layer, and the image portion and the non-image portion are substantially in the same plane, and there is a difference in ink adhesion. Is a lithographic printing plate for transferring ink to a printing medium such as paper and printing it after ink is applied only to the image line portion using. The method for producing a waterless lithographic printing plate comprises a step of exposing the direct-drawing waterless lithographic printing plate precursor of the present invention according to an image with a laser beam (exposure step), and exposing the exposed direct-drawing waterless lithographic printing plate precursor to water. Alternatively, it includes a step (developing step) of rubbing in the presence of a liquid obtained by adding a surfactant to water to remove the silicone rubber layer in the exposed portion.

  First, the exposure process will be described. The direct-drawing waterless lithographic printing plate precursor of the present invention is exposed according to an image by a laser beam scanned by digital data. When the direct-drawing waterless lithographic printing plate precursor has a protective film, it may be exposed from above the protective film, or may be exposed after peeling off the protective film. Examples of the laser light source used in the exposure step include those having an emission wavelength region in the range of 300 nm to 1500 nm. Among these, a semiconductor laser or a YAG laser having an emission wavelength region near the near infrared region is preferably used. Specifically, from the viewpoint of handling of the plate material in a bright room, laser beams having wavelengths of 780 nm, 830 nm, and 1064 nm are preferably used for exposure.

  Next, the development process will be described. The exposed original plate is rubbed in the presence of water or a solution obtained by adding a surfactant to water (hereinafter referred to as developer) to remove the silicone rubber layer in the exposed area. As the friction treatment, (i) for example, a method of wiping the plate surface with a non-woven fabric impregnated with a developer, absorbent cotton, cloth, sponge, etc., (ii) a rotating brush while pre-treating the plate surface with a developer and showering tap water, etc. (Iii) A method of jetting high-pressure water, hot water, or water vapor onto the plate surface.

  Prior to development, a pretreatment in which a plate is immersed in a pretreatment solution for a certain time may be performed. As the pretreatment liquid, for example, water or water added with a polar solvent such as alcohol, ketone, ester or carboxylic acid, polar solvent such as aliphatic hydrocarbons, aromatic hydrocarbons, etc. A solvent added or a polar solvent is used. In addition, a known surfactant can be freely added to the developer composition. As the surfactant, those having a pH of 5 to 8 when made into an aqueous solution are preferable from the viewpoints of safety and cost for disposal. The content of the surfactant is preferably 10% by weight or less of the developer. Such a developer has high safety and is preferable from the viewpoint of economy such as disposal cost. Furthermore, it is preferable to use a glycol compound or glycol ether compound as a main component, and it is more preferable that an amine compound coexists.

  Examples of the pretreatment liquid and the developer are described in JP-A-63-179361, JP-A-4-163557, JP-A-4-343360, JP-A-9-34132, and JP-A-3716429. Further, a pretreatment liquid and a developer can be used. Specific examples of the pretreatment liquid include PP-1, PP-3, PP-F, PP-FII, PTS-1, PH-7N, CP-1, NP-1, DP-1 (all of which are Toray Industries, Inc. ) Made).

  In addition, for the purpose of improving the visibility of the image area and the measurement accuracy of the halftone dots, dyes such as crystal violet, Victoria pure blue, and Astrazone red are added to these developers to develop ink reception at the same time as the development. The layer can also be dyed. Furthermore, it can also dye | stain with the liquid which added said dye after image development.

  Part or all of the development process can be automatically performed by an automatic developing machine. As an automatic processor, a device having only a developing unit, a preprocessing unit, a device in which a developing unit is provided in this order, a preprocessing unit, a developing unit, a device in which a post-processing unit is provided in this order, a preprocessing unit, a developing unit, The apparatus etc. which were provided with the post-processing part and the water washing part in this order can be used. Specific examples of such an automatic developing machine include TWL-650 series, TWL-860 series, TWL-1160 series (both manufactured by Toray Industries, Inc.), JP-A-4-2265, and JP-A-5-2272. And an automatic developing machine disclosed in Japanese Patent Laid-Open No. 5-6000. These may be used in combination.

  When the development-processed waterless planographic printing plates are stacked and stored, it is preferable to sandwich a slip sheet between the plates for the purpose of protecting the plate surface.

  Hereinafter, the present invention will be described in more detail with reference to examples. Evaluation in each Example and Comparative Example was performed by the following method.

(1) TEM observation of direct-drawing waterless lithographic printing plate precursor A sample was prepared from the direct-drawing waterless lithographic printing plate precursor before laser irradiation by an ultrathin section method, and a transmission electron microscope H-1700FA type (manufactured by Hitachi) ), The vertical and horizontal cross sections of the heat-sensitive layer of the direct-drawing waterless planographic printing plate precursor were randomly observed at 10 locations at an acceleration voltage of 100 kV and a direct magnification of 2000 times (only liquid bubble observation was 8000 times). The average film thickness of the heat-sensitive layer, the average shortest distance of the inclined region, the average area, the gradient, the area ratio, the number of liquid bubbles and the average diameter were measured by the methods described below.

(1-1) Average film thickness of heat-sensitive layer In the TEM photograph (direct magnification: 2000 times) of the vertical section of the direct-drawing waterless lithographic printing plate precursor obtained by the method described in (1) above, the flatness of the heat-sensitive layer The film thickness was measured with respect to 10 non-inclined regions, which were the parts, and the number average value was taken as the average film thickness of the heat-sensitive layer.

(1-2) Average shortest distance, average area, gradient of inclined region, and area ratio of inclined region to heat-sensitive layer surface With respect to 10 samples described in (1) above, vertical and horizontal cross sections of 100 μm ² (10 μm square) ) Of TEM observation (direct magnification: 2000 times) using the existing 3D display / analysis software to analyze the average shortest distance, average area, gradient, and slope area of the slope area. The area ratio with respect to the surface of the heat sensitive layer was measured.

(1-3) Number of liquid bubbles and average diameter In a TEM photograph (direct magnification: 8000 times) of vertical and horizontal sections of a direct-drawing waterless lithographic printing plate precursor obtained by the method described in (1) above, silicone Thermally sensitive layer 0.5 μm ³ ((longitudinal) 1 μm × (horizontal) 1 μm × (depth from the interface with the silicone rubber layer) 0 from the interface with the rubber layer to a depth of 0.5 μm 0 0.5 μm), the total number of liquid bubbles (diameter: 0.01 μm or more) was counted. The liquid bubbles on the line defining the observation area were counted when more than half of the volume of the liquid bubbles was in the observation area, and were not counted when less than half. Further, the diameters of 50 liquid bubbles randomly selected from the heat-sensitive layer in the portion where no inclined region exists were measured, and the number average value thereof was defined as the average diameter.
(2) Analysis of liquid bubbles (2-1) Pretreatment to gas chromatograph / mass measurement A direct-drawing waterless lithographic printing plate precursor cut into 1 cm ² (1 × 1 cm square) is collected in a heating glass container, and nitrogen is added. The generated gas when heated at 320 ° C. for 20 minutes while aeration of gas (flow rate: 100 ml / min) was collected in an adsorption tube (for JTD505II). This adsorption tube was heated at 320 ° C. for 15 minutes, and the thermally desorbed gas component was analyzed by gas chromatography / mass measurement. A glass container was analyzed under the same conditions as a blank.

(2-2) Gas chromatograph / mass measurement conditions Thermal desorption apparatus: JTD505II type (manufactured by Nippon Analytical Industries, Ltd.)
Secondary heat desorption temperature: 340 ° C., 180 seconds Gas chromatograph apparatus: HP5890 (manufactured by Hewlett Packard)
Column: DB-5 (manufactured by J & W)
30m × 0.25mmID, film thickness 0.5μm, US7119416H
Column temperature: 40 ° C. (4 minutes) → 340 ° C. (heating rate: 10 ° C./min)
Mass measuring device: JMS-SX102A mass spectrometer (manufactured by JEOL Ltd.)
Ionization method: EI
Scanning range: m / z 10-500 (1.2 seconds / scan)
TIC mass range: m / z 29-500.

(2-3) Preparation of calibration curve A solvent having a solubility parameter of 17.0 (MPa) ^1/2 or less used in each example and comparative example was collected in a measuring flask, and a standard solution (3375 μg / ml, 5095 μg / ml) was collected. 30265 μg / ml). From each of these standard solutions, 1 μl was sampled and analyzed under the same conditions as the sample. The absolute amount of the solvent having an injected solubility parameter of 17.0 (MPa) ^1/2 or less and a gas chromatograph / mass measurement total ion chromatogram A calibration curve was created from the relationship of peak areas.

(3) Evaluation of sensitivity and blister resistance (3-1) Evaluation of maximum blister resistance exposure The obtained direct-drawing waterless lithographic printing plate precursor (1030 × 800 mm) was used as an exposure machine “PlateRite” 8800E (large The product was mounted on Nippon Screen Manufacturing Co., Ltd., and was exposed at an irradiation energy of 80 mJ / cm ² . The surface of the full exposure plate discharged from the exposure machine was visually observed to evaluate whether the silicone rubber layer was lifted. If the silicone rubber layer was not lifted, the irradiation energy was increased by 5 mJ / cm ^{2 and} the same evaluation was performed until the silicone rubber layer was lifted. The exposure amount was defined as the maximum amount of blistering resistance.

(3-2) Evaluation of minimum reproduction amount of solid reproduction Using the automatic developing machine “TWL-1160F” (manufactured by Toray Industries, Inc.), the overall exposure plate obtained by the method described in (3-1) above, Development was performed under conditions of pretreatment liquid: none, developer: tap water (room temperature), post-treatment liquid: tap water (room temperature), and plate speed: 80 cm / min. The obtained printing plate was visually observed, and the lowest exposure amount at which the silicone rubber layer of the entire exposed portion was completely peeled was defined as the solid reproduction minimum exposure amount.

(3-3) Latitude The latitude was calculated by the following equation from the maximum blistering resistance exposure and the solid reproduction minimum exposure obtained by the above method.
Latitude (mJ / cm ² ) = Blast resistance maximum exposure (mJ / cm ² ) −Solid exposure minimum exposure (mJ / cm ² ).

Example 1
A direct-drawing waterless lithographic printing plate precursor was produced by the following production method including the step of drying the heat-sensitive layer composition solution in the presence of a solid in the heat-sensitive layer composition solution.

  The following heat insulating layer composition solution was applied on a 0.24 mm thick degreased aluminum substrate (Mitsubishi Aluminum Co., Ltd.) and dried at 200 ° C. for 90 seconds to provide a heat insulating layer having a thickness of 6.0 μm. In addition, the heat insulation layer composition solution was obtained by stirring and mixing the following components at room temperature.

<Insulation layer composition solution>
(A) Polymer having active hydrogen: Epoxy resin: “Epicoat” (registered trademark) 1010 (manufactured by Japan Epoxy Resin Co., Ltd.): 35 parts by weight (b) Polymer having active hydrogen: Polyurethane: “Samprene” (registered trademark) ) LQ-T1331D (manufactured by Sanyo Chemical Industries, solid content concentration: 20% by weight): 375 parts by weight (c) Aluminum chelate: “aluminum chelate” ALCH-TR (manufactured by Kawaken Fine Chemical Co., Ltd.): 10 weight Part (d) Leveling agent: “Disparon” (registered trademark) LC951 (manufactured by Enomoto Kasei Co., Ltd., solid content: 10% by weight): 1 part by weight (e) Titanium oxide: “Typaque” (registered trademark) CR-50 N, N-dimethylformamide dispersion (Ishihara Sangyo Co., Ltd.) (titanium oxide 50% by weight): 60 parts by weight (f) N, N-dimethylformamide: 30 parts by weight (g) Methyl ethyl ketone: 250 parts by weight Subsequently, by applying the heat-sensitive layer composition solution -1 below on the heat insulating layer, and dried by heating for 30 seconds at 120 ° C., was provided a heat-sensitive layer. The heat sensitive layer composition solution-1 was obtained by stirring and mixing the following components at room temperature.

<Thermosensitive layer composition solution-1>
(A) Infrared absorbing dye: “PROJET” 825LDI (Avecia): 6.6 parts by weight (b) Organic complex compound: Titanium-n-butoxide bis (acetylacetonate): “Narsem” (registered trademark) titanium ( Nippon Chemical Industry Co., Ltd., concentration: 73 wt%, n-butanol as a solvent (boiling point: 117 ° C., solubility parameter: 23.3 (MPa) ^1/2 ): 27 wt% included): 7.3 wt Part (c) Phenol formaldehyde novolac resin: “Sumilite Resin” (registered trademark) PR50731 (manufactured by Sumitomo Bakelite Co., Ltd., heat softening point: 95 ° C.): 49.5 parts by weight (d) Polyurethane: “Nipporan” (registered) Trademark) 5196 (manufactured by Nippon Polyurethane Co., Ltd.), concentration: 30% by weight, methyl ethyl ketone as a solvent (boiling point: 80 ° C., solubility buffer) Meter: 19.0 ^(MPa) 1/2): 35 wt%, cyclohexanone (boiling point: 155 ° C., solubility parameter: 20.3 ^(MPa) 1/2): containing 35% by weight): 13.2 parts by weight (E) Solid: Non-photosensitive crosslinked acrylic resin particle dispersion: “Lyosphere” (registered trademark) RSP3021 (manufactured by Toyo Ink Co., Ltd., average particle size: 0.6 μm, concentration: 20% by weight, dispersion medium As methyl ethyl ketone: 80% by weight): 15.0 parts by weight (f) tetrahydrofuran (boiling point: 66 ° C., solubility parameter: 18.6 (MPa) ^1/2 ): 1401.8 parts by weight (g) 17.0 ^{(MPa) equal} to or less than ^half, and the solvent consists of a liquid having a boiling point in the range of 210 to 270 ° C.: aliphatic saturated hydrocarbon: "Isopar" (trademark ) M (Esso Chemical Co., Ltd., boiling point: 223-254 ° C., solubility parameter: 14.7 (MPa) ^1/2 ): 6.6 parts by weight Next, the following silicone rubber layer composition prepared immediately before coating The solution was applied onto the heat-sensitive layer, heated at 130 ° C. for 90 seconds, and a silicone rubber layer having an average film thickness of 1.8 μm was provided to obtain a direct-drawing waterless lithographic printing plate precursor.

<Silicone rubber layer composition solution>
A bitumen dispersion was obtained by dispersing the following (a) to (c) with a bead mill “Star Mill” (registered trademark) Minizea (manufactured by Ashizawa Finetech Co., Ltd.) filled with zirconia beads (φ0.3 mm). . On the other hand, a silicone diluent was obtained by mixing (d) to (h). While stirring the bitumen dispersion, the silicone diluent was added and stirred well until uniform. The resulting liquid was naturally degassed.
(A) N650 bitumen (manufactured by Dainichi Seika Co., Ltd.): 4 parts by weight
(B) “Plenact” (registered trademark) KR-TTS (manufactured by Ajinomoto Fine Techno Co., Ltd.): 1.5 parts by weight (c) “Isopar” (registered trademark) G (manufactured by Esso Chemical Co., Ltd.): 83 wt. Part (d) α, ω-divinylpolydimethylsiloxane: “DMS” V52 (weight average molecular weight 155000, manufactured by GELEST Inc.): 83 parts by weight (e) Methylhydrogensiloxane “SH” 1107 (Toray Dow Corning Co., Ltd.) 4 parts by weight (f) vinyl tris (methylethylketooxyimino) silane: 3 parts by weight (g) platinum catalyst “SRX” 212 (manufactured by Toray Dow Corning): 6 parts by weight (h) “Isopar” (Registered) Trademark) E (Esso Chemical Co., Ltd.): 817 parts by weight The obtained direct-drawing waterless planographic printing plate precursor was subjected to TEM observation by the above method. , The heat-sensitive layer can be confirmed solids having an average particle size of 0.6 .mu.m, the average thickness of the heat-sensitive layer in a portion no solids was 0.5 [mu] m. The average shortest distance of the inclined region was 0.4 μm, the average area was 0.2 μm ² , and the inclined region having a gradient of 20 to 80 degrees was present in 70% by area or more in the entire inclined region. The area ratio of the inclined region to the surface of the heat sensitive layer was 3% by area. In addition, 42 liquid bubbles were observed in the heat-sensitive layer 0.5 μm ³ where no inclined region was present, and the average diameter of the liquid bubbles was 0.15 μm. When liquid bubbles were analyzed, the presence of a liquid having a boiling point in the range of 223 to 254 ° C. derived from “Isopar” M was confirmed, and the amount of liquid derived from “Isopar” M generated as gas was 5.34 μg. there were.
Resistant highest exposure blister fire was evaluated by the method 160 mJ / cm ^2, solid reproducibility minimum exposure amount was 140 mJ / cm ^2, had a latitude of 20 mJ / cm ^2.

(Example 2)
The heat sensitive layer composition solution-1 was changed to the following heat sensitive layer composition solution-2 in the same manner as in Example 1 except that the heat sensitive layer composition solution-1 was present in the presence of a solid in the heat sensitive layer composition solution. A direct-drawing waterless lithographic printing plate precursor was obtained by a production method including a drying step.
<Thermosensitive layer composition solution-2>
(A) "PROJET" 825LDI: 6.6 parts by weight (b) "Narsem" titanium: 7.3 parts by weight (c) "Sumilite resin" PR50731: 49.5 parts by weight (d) "Nipporan" 5196: 13 .2 parts by weight (e) Solid: Non-photosensitive crosslinked acrylic resin particle dispersion: “Riosphere” RSP3015 (manufactured by Toyo Ink Co., Ltd., average particle size: 1.4 μm, concentration: 20% by weight, dispersion medium As methyl ethyl ketone: 80% by weight): 35.0 parts by weight (f) Tetrahydrofuran: 1381.8 parts by weight (g) “Isopar” M: 6.6 parts by weight When evaluated in the same manner as in Example 1, A solid substance having an average particle size of 1.4 μm was confirmed in the heat-sensitive layer, and the average film thickness of the heat-sensitive layer where no solid substance was present was 0.5 μm. The average shortest distance of the inclined region was 1.3 μm, the average area was 1.4 μm ² , and the inclined region having a gradient of 20 to 80 degrees was present in 90% by area or more in the entire inclined region. The area ratio of the inclined region to the surface of the heat sensitive layer was 5 area%. In addition, 44 liquid bubbles were observed in the heat-sensitive layer 0.5 μm ³ in a portion where no inclined region was present, and the average diameter of the liquid bubbles was 0.15 μm. When liquid bubbles were analyzed, the presence of a liquid having a boiling point in the range of 223 to 254 ° C. derived from “Isopar” M was confirmed, and the amount of liquid derived from “Isopar” M generated as gas was 5.39 μg. there were.
The maximum blister-proof exposure dose evaluated by the above method was 180 mJ / cm ² , the solid reproduction minimum exposure dose was 140 mJ / cm ² , and had a latitude of 40 mJ / cm ² .

(Example 3)
The heat sensitive layer composition solution-1 was changed to the following heat sensitive layer composition solution-3 in the same manner as in Example 1 except that the heat sensitive layer composition solution was present in the presence of a solid in the heat sensitive layer composition solution. A direct-drawing waterless lithographic printing plate precursor was obtained by a production method including a drying step.
<Thermosensitive layer composition solution-3>
(A) "PROJET" 825LDI: 6.6 parts by weight (b) "Narsem" titanium: 7.3 parts by weight (c) "Sumilite resin" PR50731: 49.5 parts by weight (d) "Nipporan" 5196: 13 .2 parts by weight (e) Solid: Non-photosensitive crosslinked acrylic resin particle dispersion: “Lyosphere” RSP3019 (manufactured by Toyo Ink Co., Ltd., average particle size: 2.1 μm, concentration: 20% by weight, dispersion medium (Including methyl ethyl ketone: 80% by weight): 52.5 parts by weight (f) Tetrahydrofuran: 1364.3 parts by weight (g) “Isopar” M: 6.6 parts by weight When evaluated in the same manner as in Example 1, A solid substance having an average particle diameter of 2.1 μm was confirmed in the heat sensitive layer, and the average film thickness of the heat sensitive layer in the portion having no solid substance was 0.5 μm. The average shortest distance of the inclined region was 1.8 μm, the average area was 2.5 μm ² , and the inclined region having a gradient of 20 to 80 degrees was present in 90% by area or more in the entire inclined region. The area ratio of the inclined region to the surface of the heat sensitive layer was 4 area%. In addition, 40 liquid bubbles were observed in the heat-sensitive layer 0.5 μm ³ where no inclined region was present, and the average diameter of the liquid bubbles was 0.16 μm. When liquid bubbles were analyzed, the presence of a liquid having a boiling point in the range of 223 to 254 ° C. derived from “Isopar” M was confirmed, and the amount of liquid derived from “Isopar” M generated as a gas was 5.48 μg. there were.
The maximum blister-proof exposure dose evaluated by the above method was 180 mJ / cm ² , the solid reproduction minimum exposure dose was 140 mJ / cm ² , and had a latitude of 40 mJ / cm ² .

Example 4
In the same manner as in Example 1 except that the heat sensitive layer composition solution-1 was changed to the following heat sensitive layer composition solution-4, the heat sensitive layer composition solution was prepared in the presence of a solid in the heat sensitive layer composition solution. A direct-drawing waterless lithographic printing plate precursor was obtained by a production method including a drying step.
<Thermosensitive layer composition solution-4>
(A) "PROJET" 825LDI: 6.6 parts by weight (b) "Narsem" titanium: 7.3 parts by weight (c) "Sumilite resin" PR50731: 49.5 parts by weight (d) "Nipporan" 5196: 13 .2 parts by weight (e) Solid: Non-photosensitive crosslinked acrylic resin particle dispersion: “Lyosphere” RSP3009 (manufactured by Toyo Ink Co., Ltd., average particle size: 2.6 μm, concentration: 20% by weight, dispersion medium (Including methyl ethyl ketone: 80% by weight): 65.0 parts by weight (f) Tetrahydrofuran: 1351.8 parts by weight (g) “Isopar” M: 6.6 parts by weight When evaluated in the same manner as in Example 1, In the heat-sensitive layer, solids having an average particle size of 2.6 μm were confirmed, and the average film thickness of the heat-sensitive layer where no solid was present was 0.5 μm. The average shortest distance of the inclined region was 2.0 μm, the average area was 3.3 μm ² , and the inclined region having a gradient of 20 to 80 degrees was present in 90% by area or more in the entire inclined region. The area ratio of the inclined region to the surface of the heat sensitive layer was 3% by area. In addition, 46 liquid bubbles were observed in the heat-sensitive layer 0.5 μm ³ where no inclined region was present, and the average diameter of the liquid bubbles was 0.15 μm. When liquid bubbles were analyzed, the presence of a liquid having a boiling point in the range of 223 to 254 ° C. derived from “Isopar” M was confirmed, and the amount of liquid derived from “Isopar” M generated as gas was 5.56 μg. there were.
The maximum blister-proof exposure dose evaluated by the above method was 180 mJ / cm ² , the solid reproduction minimum exposure dose was 140 mJ / cm ² , and had a latitude of 40 mJ / cm ² .
(Example 5)
The heat-sensitive layer composition solution-1 was changed to the following heat-sensitive layer composition solution-5 in the same manner as in Example 1 except that the heat-sensitive layer composition solution-1 was present in the presence of a solid in the heat-sensitive layer composition solution. A direct-drawing waterless lithographic printing plate precursor was obtained by a production method including a drying step.
<Thermosensitive layer composition solution-5>
(A) "PROJET" 825LDI: 13.3 parts by weight (b) "Narsem" titanium: 14.7 parts by weight (c) "Sumilite resin" PR50731: 100.0 parts by weight (d) "Nipporan" 5196: 26 0.7 parts by weight (e) Solid: Non-photosensitive crosslinked acrylic resin particle dispersion: “Lyosphere” RSP3031 (manufactured by Toyo Ink Manufacturing Co., Ltd., average particle size: 1.7 μm, concentration: 20% by weight, dispersion medium As follows: methyl ethyl ketone: 80% by weight): 42.5 parts by weight (f) Tetrahydrofuran: 1289.5 parts by weight (g) “Isopar” M: 13.3 parts by weight When evaluated in the same manner as in Example 1, In the heat-sensitive layer, solids having an average particle diameter of 1.7 μm were confirmed, and the average film thickness of the heat-sensitive layer where no solids were present was 1.0 μm. The average shortest distance of the inclined region was 1.7 μm, the average area was 2.2 μm ² , and the inclined region having a gradient of 20 to 80 degrees was present in 90% by area or more in the entire inclined region. The area ratio of the inclined region to the surface of the heat sensitive layer was 5 area%. In addition, 40 liquid bubbles were observed in the heat-sensitive layer 0.5 μm ³ in a portion where no inclined region was present, and the average diameter of the liquid bubbles was 0.15 μm. When liquid bubbles were analyzed, the presence of a liquid having a boiling point in the range of 223 to 254 ° C. derived from “Isopar” M was confirmed, and the amount of liquid derived from “Isopar” M generated as gas was 10.75 μg. there were.

Resistant highest exposure blister fire was evaluated by the method 170 mJ / cm ^2, solid reproducibility minimum exposure amount was 130 mJ / cm ^2, had a latitude of 40 mJ / cm ^2.

(Example 6)
A direct-drawing waterless lithographic printing plate precursor was produced by the following production method including a step of applying a heat-sensitive layer composition solution onto a substrate having an inclined region on the surface.
After providing the heat insulation layer, the following solid dispersion liquid-1 was applied onto the heat insulation layer with a bar coater, dried at 200 ° C. for 30 seconds to form an inclined region on the surface of the substrate, and a thermosensitive layer composition solution thereon. A direct-drawing waterless lithographic printing plate precursor was obtained in the same manner as in Example 1 except that the following thermosensitive layer composition solution-6 was applied instead of -1.
<Solid Dispersion-1>
(A) Non-photosensitive crosslinked acrylic resin particle dispersion: “Lyosphere” RSP3015: 35.0 parts by weight (b) Methyl isobutyl ketone: 1381.8 parts by weight <Thermosensitive layer composition solution-6>
(A) "PROJET" 825LDI: 6.6 parts by weight (b) "Narsem" titanium: 7.3 parts by weight (c) "Sumilite resin" PR50731: 49.5 parts by weight (d) "Nipporan" 5196: 13 .2 parts by weight (e) Tetrahydrofuran: 1381.8 parts by weight (f) “Isopar” M: 6.6 parts by weight When evaluated in the same manner as in Example 1, the heat sensitive layer had an average particle size of 1.4 μm. Solid matter was confirmed, and the average film thickness of the heat-sensitive layer was 0.5 μm. The average shortest distance of the inclined region was 1.3 μm, the average area was 1.4 μm ² , and the inclined region having a gradient of 20 to 80 degrees was present in 90% by area or more in the entire inclined region. The area ratio of the inclined region to the surface of the heat sensitive layer was 5 area%. In addition, 43 liquid bubbles were observed in the heat-sensitive layer 0.5 μm ³ where no inclined region was present, and the average diameter of the liquid bubbles was 0.15 μm. When liquid bubbles were analyzed, the presence of a liquid having a boiling point in the range of 223 to 254 ° C. derived from “Isopar” M was confirmed, and the amount of liquid derived from “Isopar” M generated as gas was 5.43 μg. there were.
The maximum blister-proof exposure dose evaluated by the above method was 180 mJ / cm ² , the solid reproduction minimum exposure dose was 140 mJ / cm ² , and had a latitude of 40 mJ / cm ² .

(Example 7)
Except that the solid dispersion-1 was changed to the following solid dispersion-2 and the heat-sensitive layer composition solution-6 was changed to the following heat-sensitive layer composition solution-7, the same as in Example 6, A direct-drawing waterless lithographic printing plate precursor was obtained by a production method including a step of applying a heat-sensitive layer composition solution onto a substrate having an inclined region on the surface.
<Solid dispersion-2>
(A) Non-photosensitive crosslinked acrylic resin particle dispersion: “Lyosphere” RSP3009: 65.0 parts by weight (b) Methyl isobutyl ketone: 1351.8 parts by weight <Thermosensitive layer composition solution-7>
(A) "PROJET" 825LDI: 6.6 parts by weight (b) "Narsem" titanium: 7.3 parts by weight (c) "Sumilite resin" PR50731: 49.5 parts by weight (d) "Nipporan" 5196: 13 .2 parts by weight (e) Tetrahydrofuran: 1351.8 parts by weight (f) “Isopar” M: 6.6 parts by weight When evaluated in the same manner as in Example 1, the heat sensitive layer had an average particle size of 2.6 μm. Solid matter was confirmed, and the average film thickness of the heat-sensitive layer was 0.5 μm. The average shortest distance of the inclined region was 2.0 μm, the average area was 3.3 μm ² , and the inclined region having a gradient of 20 to 80 degrees was present in 90% by area or more in the entire inclined region. The area ratio of the inclined region to the surface of the heat sensitive layer was 3% by area. In addition, 45 liquid bubbles were observed in the heat-sensitive layer 0.5 μm ³ where no inclined region was present, and the average diameter of the liquid bubbles was 0.15 μm. When liquid bubbles were analyzed, the presence of a liquid having a boiling point in the range of 223 to 254 ° C. derived from “Isopar” M was confirmed, and the amount of liquid derived from “Isopar” M generated as gas was 5.36 μg. there were.
The maximum blister-proof exposure dose evaluated by the above method was 180 mJ / cm ² , the solid reproduction minimum exposure dose was 140 mJ / cm ² , and had a latitude of 40 mJ / cm ² .

(Example 8)
A direct-drawing waterless lithographic printing plate precursor was produced by the following production method including a step of applying a heat-sensitive layer composition solution onto a substrate having an inclined region on the surface.
After the heat insulation layer is provided, the surface of the heat insulation layer is cut with a single crystal diamond tool (UPC-T manufactured by Allied Material Co., Ltd., minimum tip width: 0.5 μm, edge angle: 20 ° or more), and striped on the substrate surface. Direct-drawing waterless lithographic printing plate precursor in the same manner as in Example 1 except that an inclined region was formed, and the following thermal layer composition solution-8 was applied thereon instead of the thermal layer composition solution-1. Got.
<Thermosensitive layer composition solution-7>
(A) "PROJET" 825LDI: 41.3 parts by weight (b) "Narsem" titanium: 45.5 parts by weight (c) "Sumilite resin" PR50731: 309.6 parts by weight (d) "Nipporan" 5196: 82 0.7 parts by weight (e) Tetrahydrofuran: 979.6 parts by weight (f) “Isopar” M: 41.3 parts by weight When evaluated in the same manner as in Example 1, the average thickness of the heat-sensitive layer was 3.0 μm. there were. The average shortest distance of the inclined region was 0.2 μm, and the inclined region having a gradient of 20 to 80 degrees was present in 60% by area or more in the entire inclined region. The area ratio of the inclined region to the surface of the heat sensitive layer was 1 area%. In addition, 46 liquid bubbles were observed in the heat-sensitive layer 0.5 μm ³ where no inclined region was present, and the average diameter of the liquid bubbles was 0.16 μm. When liquid bubbles were analyzed, the presence of a liquid having a boiling point in the range of 223 to 254 ° C. derived from “Isopar” M was confirmed, and the amount of liquid derived from “Isopar” M generated as gas was 5.55 μg. there were.
Resistant highest exposure blister fire was evaluated by the method 135mJ / cm ^2, solid reproducibility minimum exposure amount was 130 mJ / cm ^2, had a latitude of 5 mJ / cm ^2.

Example 9
A direct-drawing waterless lithographic printing plate precursor was produced by the following production method including a step of deforming or removing part of the heat-sensitive layer.
After providing a heat insulating layer in the same manner as in Example 1, the following thermal layer composition solution-9 was applied, and an imprint mold having pillars (NIM-PH1000 manufactured by NTT-AT Nanofabrication Co., Ltd., material) : Quartz, pillar: height 1 μm × diameter 1 μm, duty ratio: 16.67%), pressed against the surface of the coating film, dried at 120 ° C. for 180 seconds, then removed the imprint mold, and the heat sensitive layer A depressed structure was formed on the surface. Next, a silicone rubber layer was provided in the same manner as in Example 1 to obtain a direct-drawing waterless lithographic printing plate precursor.
<Thermosensitive layer composition solution-9>
(A) "PROJET" 825LDI: 20.7 parts by weight (b) "Narsem" titanium: 22.8 parts by weight (c) "Sumilite resin" PR50731: 154.8 parts by weight (d) "Nipporan" 5196: 41 .4 parts by weight (e) Methyl ethyl ketone: 826.4 parts by weight (f) Methyl isobutyl ketone: 413.2 parts by weight (g) “Isopar” M: 20.7 parts by weight Evaluation was performed in the same manner as in Example 1. The average film thickness of the heat sensitive layer was 1.5 μm. The average shortest distance of the inclined region was 1.0 μm, the average area was 1.6 μm ² , and the inclined region having a gradient of (angle of depression) of 20 to 80 degrees was present in 80% by area or more in the entire inclined region. The area ratio of the inclined region to the surface of the heat sensitive layer was 17 area%. In addition, 43 liquid bubbles were observed in the heat-sensitive layer 0.5 μm ³ where no inclined region was present, and the average diameter of the liquid bubbles was 0.15 μm. When the liquid bubbles were analyzed, the presence of a liquid having a boiling point in the range of 223 to 254 ° C. derived from “Isopar” M was confirmed, and the amount of liquid derived from “Isopar” M generated as gas was 5.41 μg. there were.
The maximum blister-proof exposure dose evaluated by the above method was 170 mJ / cm ² , the solid reproduction minimum exposure dose was 140 mJ / cm ² , and had a latitude of 30 mJ / cm ² .

(Example 10)
The heat sensitive layer composition solution-9 was changed to the following heat sensitive layer composition solution-10, and the imprint mold having pillars was changed to an imprint mold having holes (NIM-PH1000 manufactured by NTT-AT Nanofabrication Co., Ltd.). , Material: quartz, hole: depth 1 μm × diameter 1 μm, duty ratio: 16.67%), except that a raised structure was formed in the heat sensitive layer instead of the depressed structure, A direct-drawing waterless lithographic printing plate precursor was obtained by a production method including a step of deforming or removing part of the heat-sensitive layer.
<Thermosensitive layer composition solution-10>
(A) "PROJET" 825LDI: 55 parts by weight (b) "Narsem" titanium: 60.6 parts by weight (c) "Sumilite resin" PR50731: 412.8 parts by weight (d) "Nipporan" 5196: 110.2 Parts by weight (e) methyl ethyl ketone: 537.6 parts by weight (f) methyl isobutyl ketone: 268.8 parts by weight (g) “Isopar” M: 55 parts by weight When evaluated in the same manner as in Example 1, The average film thickness was 3.0 μm. The average shortest distance of the inclined region was 1.0 μm, the average area was 1.6 μm ² , and the inclined region having a gradient of 20 to 80 degrees was present in 60% by area or more in the entire inclined region. The area ratio of the inclined region to the surface of the heat sensitive layer was 17 area%. In addition, 48 liquid bubbles were observed in the heat-sensitive layer 0.5 μm ³ where there is no inclined region, and the average diameter of the liquid bubbles was 0.16 μm. When liquid bubbles were analyzed, the presence of a liquid having a boiling point in the range of 223 to 254 ° C. derived from “Isopar” M was confirmed, and the amount of liquid derived from “Isopar” M generated as gas was 5.60 μg. there were.
Resistant highest exposure blister fire was evaluated by the method 160 mJ / cm ^2, solid reproducibility minimum exposure amount was 150 mJ / cm ^2, had a latitude of 10 mJ / cm ^2.

(Example 11)
A direct-drawing waterless lithographic printing plate precursor was produced by the following production method including a step of deforming or removing part of the heat-sensitive layer.
The surface of the heat-sensitive layer formed by changing the heat-sensitive layer composition solution-1 to the following heat-sensitive layer composition solution-11, a single crystal diamond bite (UPC-T manufactured by Allied Material Co., Ltd., minimum tip width: 0.5 μm, A direct-drawing waterless lithographic printing plate precursor was obtained in the same manner as in Example 1 except that the inclined region was formed in a stripe shape in the heat-sensitive layer by cutting at a cutting edge angle of 20 ° or more.
<Thermosensitive layer composition solution-11>
(A) "PROJET" 825LDI: 20.7 parts by weight (b) "Narsem" titanium: 22.8 parts by weight (c) "Sumilite resin" PR50731: 154.8 parts by weight (d) "Nipporan" 5196: 41 .4 parts by weight (e) Tetrahydrofuran: 1239.6 parts by weight (f) “Isopar” M: 20.7 parts by weight When evaluated in the same manner as in Example 1, the average thickness of the thermosensitive layer was 1.5 μm. there were. The average shortest distance of the inclined region was 1.0 μm, and the inclined region having a gradient of (an depression angle) of 20 to 80 degrees was 90% by area or more in the entire inclined region. The area ratio of the inclined region to the surface of the heat sensitive layer was 10% by area. In addition, 44 liquid bubbles were observed in the heat-sensitive layer 0.5 μm ³ in a portion where no inclined region was present, and the average diameter of the liquid bubbles was 0.15 μm. When liquid bubbles were analyzed, the presence of a liquid having a boiling point in the range of 223 to 254 ° C. derived from “Isopar” M was confirmed, and the amount of liquid derived from “Isopar” M generated as gas was 5.45 μg. there were.
The maximum blister-proof exposure dose evaluated by the above method was 180 mJ / cm ² , the solid reproduction minimum exposure dose was 140 mJ / cm ² , and had a latitude of 40 mJ / cm ² .

(Example 12)
Example 10 except that the heat-sensitive layer composition solution-1 was changed to the following heat-sensitive layer composition solution-12 and the single crystal diamond tool was changed to UPC-Nano Groove (blade width: 5 μm) manufactured by Allied Materials Co., Ltd. In the same manner as described above, a direct-drawing waterless lithographic printing plate precursor was obtained by a production method including a step of deforming or removing part of the heat-sensitive layer.
<Thermosensitive layer composition solution-12>
(A) "PROJET" 825LDI: 41.3 parts by weight (b) "Narsem" titanium: 45.5 parts by weight (c) "Sumilite resin" PR50731: 309.6 parts by weight (d) "Nipporan" 5196: 82 0.7 parts by weight (e) Tetrahydrofuran: 979.6 parts by weight (f) “Isopar” M: 41.3 parts by weight When evaluated in the same manner as in Example 1, the average thickness of the heat-sensitive layer was 3.0 μm. there were. The average shortest distance of the inclined region was 5.0 μm, and the inclined region having a gradient of (an depression angle) of 20 to 80 degrees was present in 60% by area or more in the entire inclined region. The area ratio of the inclined region to the surface of the heat sensitive layer was 30 area%. In addition, 45 liquid bubbles were observed in the heat-sensitive layer 0.5 μm ³ where no inclined region was present, and the average diameter of the liquid bubbles was 0.15 μm. When liquid bubbles were analyzed, the presence of a liquid having a boiling point in the range of 223 to 254 ° C. derived from “Isopar” M was confirmed, and the amount of liquid derived from “Isopar” M generated as gas was 5.58 μg. there were.
Resistant highest exposure blister fire was evaluated by the method 200 mJ / cm ^2, solid reproducibility minimum exposure amount is 195mJ / cm ^2, it had a latitude of 5 mJ / cm ^2.

(Comparative Example 1)
A direct-drawing waterless lithographic printing plate precursor was obtained in the same manner as in Example 1 except that the heat-sensitive layer composition solution-1 was changed to the following heat-sensitive layer composition solution-13.
<Thermosensitive layer composition solution-13>
(A) "PROJET" 825LDI: 6.9 parts by weight (b) "Narsem" titanium: 7.6 parts by weight (c) "Sumilite resin" PR50731: 51.6 parts by weight (d) "Nipporan" 5196: 13 .8 parts by weight (e) Tetrahydrofuran: 1413.2 parts by weight (g) “Isopar” M: 6.9 parts by weight When evaluated in the same manner as in Example 1, no inclined region was observed on the surface of the thermosensitive layer. . The average film thickness of the heat sensitive layer was 0.5 μm. Moreover, 41 liquid bubbles were observed in the thermosensitive layer 0.5 μm ³ , and the average diameter of the liquid bubbles was 0.15 μm. When the liquid bubbles were analyzed, the presence of a liquid having a boiling point in the range of 223 to 254 ° C. derived from “Isopar” M was confirmed, and the amount of liquid derived from “Isopar” M generated as gas was 5.32 μg. there were.
The maximum blister-proof exposure dose evaluated by the above method was 140 mJ / cm ² , the solid reproduction minimum exposure dose was 140 mJ / cm ² , and had no latitude.

(Comparative Example 2)
A direct-drawing waterless lithographic printing plate precursor was obtained in the same manner as in Example 1 except that the heat-sensitive layer composition solution-1 was changed to the following heat-sensitive layer composition solution-14.
<Thermosensitive layer composition solution-14>
(A) "PROJET" 825LDI: 20.7 parts by weight (b) "Narsem" titanium: 22.8 parts by weight (c) "Sumilite resin" PR50731: 154.8 parts by weight (d) "Nipporan" 5196: 41 .4 parts by weight (e) Tetrahydrofuran: 1239.6 parts by weight (g) “Isopar” M: 20.7 parts by weight When an initial evaluation was performed in the same manner as in Example 1, no inclined region was observed on the surface of the thermosensitive layer. It was. The average thickness of the heat sensitive layer was 1.5 μm. Further, 44 liquid bubbles were observed in the heat-sensitive layer 0.5 μm ³ , and the average diameter of the liquid bubbles was 0.15 μm. When liquid bubbles were analyzed, the presence of a liquid having a boiling point in the range of 223 to 254 ° C. derived from “Isopar” M was confirmed, and the amount of liquid derived from “Isopar” M generated as gas was 5.38 μg. there were.
The maximum blister-proof exposure dose evaluated by the above method was 130 mJ / cm ² , the solid reproduction minimum exposure dose was 130 mJ / cm ² , and had no latitude.

  Table 1 shows the evaluation results of Examples 1 to 12 and Comparative Examples 1 and 2.

  The direct-drawing waterless planographic printing plate precursor of the present invention can be used in general printing fields (commercial printing, newspaper printing, printing on non-absorbent materials such as films, resin plates, and metals). Further, the present invention can be applied to the display field such as PDP and LCD, and the printable electronics field in which a wiring pattern is produced by a printing method.

Claims (4)

A direct-drawing waterless lithographic printing plate precursor having at least a heat-sensitive layer and a silicone rubber layer in this order on a substrate, having an inclined region on the surface of the heat-sensitive layer facing the silicone rubber layer, and having the inclined region A direct-drawing waterless lithographic printing plate precursor having an area ratio of 1% by area or more relative to the surface of the heat-sensitive layer. A method for producing a direct-drawing waterless lithographic printing plate precursor comprising at least a step of forming a heat-sensitive layer and a step of forming a silicone rubber layer on a substrate, wherein the step of forming the heat-sensitive layer forms the heat-sensitive layer. The method for producing a direct-drawing waterless lithographic printing plate precursor according to claim 1, comprising a step of drying the heat-sensitive layer composition solution in the presence of a solid in the heat-sensitive layer composition solution. A method for producing a direct-drawing waterless lithographic printing plate precursor comprising at least a step of forming a heat-sensitive layer and a step of forming a silicone rubber layer on a substrate, wherein the step of forming the heat-sensitive layer comprises an inclined region on the surface The method for producing a direct-drawing waterless lithographic printing plate precursor according to claim 1, comprising a step of applying a heat-sensitive layer composition or a heat-sensitive layer composition solution onto a substrate having a surface. A method for producing a direct-drawing waterless lithographic printing plate precursor comprising at least a step of forming a heat-sensitive layer on a substrate and a step of forming a silicone rubber layer, and further a step of deforming or removing a part of the heat-sensitive layer The method for producing a direct-drawing waterless lithographic printing plate precursor according to claim 1, comprising: